CA2060276A1 - Stabilised polyolefin - Google Patents
Stabilised polyolefinInfo
- Publication number
- CA2060276A1 CA2060276A1 CA002060276A CA2060276A CA2060276A1 CA 2060276 A1 CA2060276 A1 CA 2060276A1 CA 002060276 A CA002060276 A CA 002060276A CA 2060276 A CA2060276 A CA 2060276A CA 2060276 A1 CA2060276 A1 CA 2060276A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkyl
- formula
- radical
- phenyl
- 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.)
- Abandoned
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 42
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000477 aza group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 170
- 125000000217 alkyl group Chemical group 0.000 claims description 84
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 62
- 239000001257 hydrogen Substances 0.000 claims description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims description 51
- -1 -COOR'4 Chemical group 0.000 claims description 42
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 42
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 2
- MALIONKMKPITBV-UHFFFAOYSA-N 2-(3-chloro-4-hydroxyphenyl)-n-[2-(4-sulfamoylphenyl)ethyl]acetamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1CCNC(=O)CC1=CC=C(O)C(Cl)=C1 MALIONKMKPITBV-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005936 piperidyl group Chemical group 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims 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 claims 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 24
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000003019 stabilising effect Effects 0.000 abstract description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000005507 spraying Methods 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
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003490 Thiodipropionic acid Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940063583 high-density polyethylene Drugs 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FPQJEXTVQZHURJ-UHFFFAOYSA-N n,n'-bis(2-hydroxyethyl)oxamide Chemical compound OCCNC(=O)C(=O)NCCO FPQJEXTVQZHURJ-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- OUBISKKOUYNDML-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-[bis[2-oxo-2-(2,2,6,6-tetramethylpiperidin-4-yl)oxyethyl]amino]acetate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CN(CC(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 OUBISKKOUYNDML-UHFFFAOYSA-N 0.000 description 1
- 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
- ATLWFAZCZPSXII-UHFFFAOYSA-N (2-octylphenyl) 2-hydroxybenzoate Chemical compound CCCCCCCCC1=CC=CC=C1OC(=O)C1=CC=CC=C1O ATLWFAZCZPSXII-UHFFFAOYSA-N 0.000 description 1
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical class CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 1
- GOZHNJTXLALKRL-UHFFFAOYSA-N (5-benzoyl-2,4-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(O)=C(C(=O)C=2C=CC=CC=2)C=C1C(=O)C1=CC=CC=C1 GOZHNJTXLALKRL-UHFFFAOYSA-N 0.000 description 1
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-UHFFFAOYSA-N 0.000 description 1
- KEXRSLVRFLEMHJ-UHFFFAOYSA-N 1-o,4-o-bis[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl] benzene-1,4-dicarbothioate Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1COC(=S)C1=CC=C(C(=S)OCC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C=C1 KEXRSLVRFLEMHJ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- IOHCSOXUCWUZQJ-UHFFFAOYSA-J 2,2'-spirobi[1,3,2-benzodioxastannole] Chemical compound O1c2ccccc2O[Sn]11Oc2ccccc2O1 IOHCSOXUCWUZQJ-UHFFFAOYSA-J 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- UUAIOYWXCDLHKT-UHFFFAOYSA-N 2,4,6-tricyclohexylphenol Chemical compound OC1=C(C2CCCCC2)C=C(C2CCCCC2)C=C1C1CCCCC1 UUAIOYWXCDLHKT-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
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 1
- GTIBACHAUHDNPH-UHFFFAOYSA-N n,n'-bis(benzylideneamino)oxamide Chemical compound C=1C=CC=CC=1C=NNC(=O)C(=O)NN=CC1=CC=CC=C1 GTIBACHAUHDNPH-UHFFFAOYSA-N 0.000 description 1
- ZJFPXDGPJMHQMW-UHFFFAOYSA-N n,n'-bis[3-(dimethylamino)propyl]oxamide Chemical compound CN(C)CCCNC(=O)C(=O)NCCCN(C)C ZJFPXDGPJMHQMW-UHFFFAOYSA-N 0.000 description 1
- JVKWTDRHWOSRFT-UHFFFAOYSA-N n-(4-hydroxyphenyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 JVKWTDRHWOSRFT-UHFFFAOYSA-N 0.000 description 1
- YASWBJXTHOXPGK-UHFFFAOYSA-N n-(4-hydroxyphenyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 YASWBJXTHOXPGK-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NTTIENRNNNJCHQ-UHFFFAOYSA-N octyl n-(3,5-ditert-butyl-4-hydroxyphenyl)carbamate Chemical compound CCCCCCCCOC(=O)NC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NTTIENRNNNJCHQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 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
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([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
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- C08K5/1535—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Stabilised polyolefin Abstract of the disclosure Combinations of compounds of the formula
Description
~ D ~
Stabilised polvole~m Tlle present invention relates to a polyolefin stabilised against thennal, oxidative andlor ` actinic degradation, which comprises a benzofuran-2-one and a phosphite or/and phosphonite as stabiliser.
.
The use of benzofuran-2-ones as stabilisers for polyolefins is described, for example, in US-A-4,32~,863 and US-A-4,338,244. According to these publications, these compounds are usually added to the polyole~ln in amounts of 0.01 to 5 %, relative to dle total weight of the material to be stabilised. Surprisingly, it has now been found that benzofuran-2-ones are also capable of effectively stabilising polyole~ms even in much lower concentrations if used together with phosphites, phosphonites or aza analogs thereof. In particular, this also effectively reduces the yellowing of the polyolefins during processing.
Accordingly, the present invention relates to a polyole~ln containing, as stabiliser, a mixture comprising at least one phosphite or phosphonite or aza analogs thereof and at least one benzofuran-2-one in an amount of 0.0001 to O.OlS % by weight of the formula Rs R3 ~ C = O
ill which Rl is phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine, R2 is hydrogen and R4 is hydrogen, alkyl having 1 tO 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenylalkyl having 1 to 12 carbon atoms in the alkyl moiety or chlorine, ~6~
R3 has the meaning of R2 or R4 or is a radical of the formula -(CH2~-OR6, O O O
-(CH23~-N(R7)2. ~cH2~-o-A-o-c~cH2 n~E, ~CH2~-NR8-A-NR8-C~CH2 n~E~ iCH2~C-NRg-A-O-(~CH2 n~E-~CH2~C--N N--c~CH2~ E, -CH2-S-R9, -CH(C6Hs)- ~OR6 or -D-E, in which R6 is hydrogen, aLlcyl having 1 to 18 carbon atoms, aLIcyl having 2 to 18 c~rbon atoms and interrupted by oxygen or sulfur, dialkylaminoaLkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, n is 0, 1 or 2, the substituents R7 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, a radical of the forrnula -C2H40H, ~C2H4~0~CmH2m~l or -C2H4-O-~-RIo or together with the nitrogen atom to which they are bound form a piperidine or morpholine radical, m is 1 to 18, Rlo is hydrogen, aLkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms, A is an alkylene having 2 to 22 carbon atoms, which may be interrupted by nitrogen, oxygen or sulfur, R8 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a ~otal of at most 16 carbon atoms, or benzyl, Rg is alkyl having 1 to 18 carbon atoms, D is -O-, -S-, -SO-, -SO2- or -C(Rll)2-, the substituents Rll are, independently of one another, hydrogen, alkyl having a total of at ` 20~(~2~3 .~
., O
most 16 carbon atoms, phenyl or a radical of the formula tCH~-OR6 or O
tCH2~-N(R7)2. or together with the carbon atom to which they are bound form a cycloalkyl having 5 to 7 carbon atoms, in which n, R6 and R7 are as defined, E is a radical of the formula ~C/
/ \
R2 H Rl hl which Rl, R2 and R4 are as defined, and Rs is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a O O
radical of the formula -CH2-~-OR6 or -CH2- ~-N(R7)2, in which R6 and R7 are as defined, or Rs together with R4 forms a tetramethylene radical.
The present invention also relates to a process for the stabilisation of polyolefins, which comprises incorporadng therein or applying thereto a stabiliser mixture as defined above.
The benzofuran-2-ones of the formula (1) and processes for their preparation are described in the mentioned IJS-A-4,325,863 and US-A-4,338,244. US-A-4,374,219; 4,318,845;
4,386,204; 4,409,346; 4,322,527; 4,661,594 and 4,407,976 have disclosed, for example, the phosphorus compounds of the formulae (2) to (14) and also processes for their preparation.
Alkyl substituents in the compounds of the formula (1) can contain up to 22 carbon atoms.
Exarnples of these are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl and the corresponding branched isomers, in particular tert-butyl, i-octyl and i-dodecyl. Alkoxy and alkoxycarbonyl radicals are derived from these groups as are the alkylene radicals which are contained in the definitions of the substituents shown in formula (1). The alkyl radicals : 2~2~
listed can be interrupted by oxygen or sulfur, in order to form in particular structural units such as -CH2CH2-O-CH2CH2-, -CH2CH2-S-CH2CH2- or -O-(CH2)6-O-. Alkyl radicals as substituents on the phenyl rings preferably occupy the 3 and 5 positions.
The compounds of the formula (1) are incorporated into the polyolefin in an amount of 0.0001 to 0.015 % by weight, relative to the total weight of the ma~erial to be stabilised, and preferably of 0.0001 to 0.012, in particular 0.0001 to 0.008, % by weight. Aparticularly preferred amount is the range from 0.0005 to 0.007, in particular 0.0005 to 0.005, % by weight.
~, Suitable substituents for the phosphorus compounds of the formulae (2) to (14) are, inter alia, alkyl radicals having up to 20 carbon atoms. These radicals and those alkyl groups which are intermpted by sulfur, oxygen or nitrogen-containing groups correspond to the alkyl substituents already mentioned. Examples of cycloalkyl radicals containing 5 to 8 carbon atoms are cyclopentyl, cyclohexyl and cyclooctyl.
Polyolefins according to the invention preferably contain 0.01 to 2, in paIticular 0.01 to 1, % by weight, relative to the total weight of the material to be stabilised, of phosphite or phosphonite or aza analog thereof, preferably one or more compounds of the formulae (2) to (14).
R3 is preferably hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula tCH2~-OR6 ~ tCH23~-N(R7)2 or -D-E~
in which n, R6, R7, D and E are as defined. R6 is preferably hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.
In A further group of preferably used benzofuran-2-ones, Rl is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms. R2 is hydrogen and R4 is hydrogen or alkyl having 1 to 12 carbon atoms, R3 is hydrogen, alkyl O O
having 1 to 12 carbon atoms, tCH2~C-OR6, tCH2~-N(R7)2 or -D-E, Rs is hydrogen, aL~cyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, -CH2-C-OR6 or 2 ~ 7 $
,. 5 .
-CH2-~-N(R7)2, or Rs together with R4 is tetramethylene, and n, R6, R7, D and E are as defined. Of these, preference is given to those compounds of the folmula (1) in which Rl is phenyl, R3 is hydrogen, aLl~yl having 1 to 12 carbon atoms or -D-E, R2 is hydrogen and R4 is hydrogen or alkyl having 1 to 4 carbon atoms, and Rs is aLlcyl having 1 to 20 carbon atoms, cyclopentyl or cyclohexyl, D and E being as def1ned, and in particular to those compounds in which Rl is phenyl, R3 is aLl~yl having 1 to 4 carbon atoms or -D-E, R2 and R4 are hydrogen, and Rs is aL~cyl having 1 to 4 carbon atoms or cyclopentyl or cyclohexyl, I) being -C(Rli)2- and E being a radical of the formula ~ \C o ~f /c\
in which the substituents Rl 1 are identical to or different from one another and are each allyl having 1 to 4 carbon atoms, and Rl, R2, R4 and Rs are as de~med.
The phosphites to be used according to the invention or aza analogs thereof preferably have the formula ~OR2 ~OR2 (2) RiO-P~ , (3) A - ~) p\
OR3 OR3 n' (4) (R~lo)m~-p(NR7Rs)3-m~ (5) A ~O-P(NR 7R 8)2) D~o/ 1~ ~ (7) ~ P--O~ A' 2~6~27~
H C>CO\ R' H C>~
H3C / ~R'11 H3C d (10) R'l3--X--P ~)C P--X-R'l3 or ` O O
R~
~ /f~R'14\
(11)W~
in which R'l, R'2 and R'3, independently of one another, are aLkyl having 1 to 18 carbon atoms, allyl having 1 to 18 carbon atoms which is substituted by halogen, -COOR'4, -CN or -CONR'4R'4, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR'4-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms, 2,2,6,6-tetramethylpiperid-4-yl, N-allyl- or N-benzyl- or N-alkyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety or N-alkanoyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety, or N-alkylene-2,2,6,6-tetramethylpiperidyl or N-alkylene-4-alkoxy-2,2,6,6-tetramethyl-piperidyl having 1 to 3 carbon atoms in the alkylene moiety and 1 to 18 carbon atoms in the alkoxy moiety, R'4 or the radicals R'4 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms orphenylalkyl ha-ving 1 to 4 carbon atoms in the alkyl moiety, n'is2,30r4, A' is alkylene having 2 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or -NR'4-, in which R'4 is as defined, or a radical af the formula 2~2~
., R's R~5 ~~ or {}B {~
,. R'6 R'6 if n'is2, A' is a radical of the formula ~C~H2r l- or N(C~H2CH2~, in which r is 5 or 6, if n' is 3, A' is the radical of the formula C(CH2~, if n' is 4, R's and R'6, independently of one another, are hydrogen or alkyl having 1 to 8 carbon ~toms, A" has the meaning of A', if n' is 2, B is a radical of the formula -CH2-, -CHR'4-, -(:IR~lR'4-, -S- or a direct ~ond, in which R' and R'4 are as defined, m' is 1 or 2, R'7 and R'8, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'7 or R'8 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-, p is 1 or 2, D' is methyl, if p is 1, and is -CH20CH2-, if p is 2, R'9 is methyl and R'lo has the meaning of R'l, qis20r3, R'll and R'l2, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R' ~md R'l2 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-0-CH2CH2-, or R'll is a radical of the formula / ~ CH3 --E'- Y1--P~
o / C~13 in which E' is alkylene having 2 to 18 carbon atoms or alkylene having 2 to 18 carbon atoms and interrupted by -S-, -0- or -NR',2-, in which R',2 is as defined, X and Yl, independently of one another, are -0- or -NR'12-, in which R'12 is as de~med, 2 ~ ~
R'13, when X is -O-, has the meani~g of R'l, and R'13, when X is -NR'12-, has the meanin5 of R'12, y is 1, 2 or 3, W is alkyl having 1 to 18 carbon atoms, a radical of the formula -OR'I6, -NR'17R'18 or fluorine, if y is 1, W is a radical of the formula -O-A"-O-, -NR'17-A"'-NR',7-, -O-A"'-NR'17- or H ~CyCH3 --O~<N--CH2--CH--Rlg~
if yis2, W is a radical of the formula R4C~CH20~, N(C2H40~ or N(C3H60~, in which R'4 is as defined, if y is 3, R'l6 has the meaning of R l.
R'l7 and R',8, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,~,6-pentamethylpiperid-4-yl radical, or R'17 and R'lg together form butylene, pentylene, hexylene or the radical of ~e fonnula -CH2C~12-O-C~H2CH2-~A" is as defined, A"' is alkylene having 2 to 12 carbon atoms or aLkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or NR'4-, in which R'4 is as defined, R'lg is hydrogen or methyl, the substituents R'l4 are, independently of one another, hydrogen, aLIcyl having 1 to 9 carbon stoms or cyclohexyl, R'l5 is hydrogen or methyl and Z is a direct bond, -~EI2-, -C(R'I4)2- or -S-, in which the substituents R~l4 are identical or different and are as deflned.
Particularly suitable phosphites have the formula (2), (3), (6), (B), (10) or (11).
Preferred phosphites of the formula (2) are those in which R'l, R'2 and R'3, independently of one another7 are alkyl having 1 to 18 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or 2,2,6,6-tetramethylpiperid-4-yl, in particular phenyl which is substituted, independently of ?,G6027~
. .
~ one another by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
.,~
In phosphites of the formula (3), A' is preferably alkylene having 2 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms, -CH2CH2-O-CH2CH2-, -CH2OEI2-O-CH2CH20-CH2CH2- or -CH2CH2-NR'~-CH2CH2-, if n' is 2, or A' is N(CH2CH2~, in which R'4 is alkyl having 1 to 4 carbon atoms, if n' is 3.
Phosphites of the formula (6) are preferred, if p is 1, D' is methyl, R'g is methyl and R'lo is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms.
Particularly suitable phosphites of the formula t8) are those in which R'~l and R'~2, independently of one another, are a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R'll is a radical of the formula / ~ CH3 --E'--N--P ~<CH3 ' in which E' is aLtcylene having 2 to 6 carbon atoms and R'l2 is as defined.
P~rticularly suitable phosphites of the formula (10) are those in which R'13-X- is a radical of the formula -N(~',2)2 or phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, in which the substituents R'12 are, independently of one ,another, alkyl having 1 to 12 carbon atoms or a 2,2,6,6-tetra- or 1,'~,2,6,6-pentamethylpiperid-4-yl radical, in particular in which R'13-~- is phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
Preferably, phosphites of the formula (11) are used in which W is a radical of the forrnula -OR'16, -NR'l7R'l8 or fluorine, if y is 1, or W is a radical of the formula -O-CH2CH2-NR'4-CH2CH2-O-, if y is 2, or W is a radical of the fonnula N(CH2CH20~, if y is 3, in which R'l6 is alkyl having 1 to 18 carbon atoms, R' ~7 and R'l8, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'l7 and R'l8 together forrn a piperidyl, morpholinyl or hexamethyleneimino radical, and R'4 is as defined, Z is a direct bond, -CH2- or -CHCH3-, and the two substituents R'14 are, independently of one another, alkyl having 1 to 4 carbon atoms, and in particular those in which W is 2-ethylhexoxy or fluorine, R'14 is tert-butyl, R'ls is hydrogen and ~ is -CH2- or -CH(CH3)-, if y is 1, or W is a radical of the formula -O-CH2CH2-NCH3-CH2CH2-O-, if y is 2.
Suitable phosphonites or aza analogs thereof are preferably those of the formulae (12) Hsc6-p(oR2o)s(NR2lR22)2-s~
/ R24~
(13) ~ R25 G f t Kand \~4~O /
R24 k (14) R21~0 ~ p~O~R~227 in which R20 is alkyl having 1 to 20 carbon atoms, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR26-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or is 2,2,6,6-tetramethylpiperid-4-yl, R26 is alkyl having 1 to 4 carbon atoms, and R2l and R22, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R21 and R22 together forrn butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2-CH2-.
s is 1 or 2, the substituents R24 are, independently of one another, hydrogen, alkyl having 1 to 12 carbon atoms or cyclohexyl, 2 ~ 7 ~
:`
R25 is hydrogen or methyl, G is a direct bond, -CH2-, -C(R24)2- or -S-, in which the substituents R24 are identical or different and are as defined, k is 1 or 2, K is phenyl or naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, if k is 1, or K is phenylene or biphenylene, if k is 2, R27 and R28, independently of one another, are phenyl, naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms and in particular those of the formula (12) in which R20 is alkyl having 1 to 20 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, and R2l and R22, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl or cyclohexyl, or R21 and R22 together form pentylene, hexylene or the radical of the formula -CH2CH2-O-C~2CH2-. Particularly preferred are compounds in which R20 is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
Particularly suitable phosphonites of the foimula (13) are those in which the substituents R24 are, independently of one another, alkyl having 1 to 12 carbon atoms, G is a direct bond or -CH2- and k is 1.
In preferred phosphonites of the formula (14), R27 and R28 are, independently of one another, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 8 carbon atoms.
Furthermore, it has been shown that in certain cases the additional use of at least one costabiliser, in particular a phenolic antioxidant, can have advantageous effects. Examples are:
1. Antioxidants 1.1. Alkvlated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(c~-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, ~6~2~
.
; -12-2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.
1.2. Alkvlated hvdro~uinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.
1.3. Hvdroxylated thiodiphenvl ethers, for exarnple 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis~4-octylphenol), 4,4'-thiobis(6-~ert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2 '-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenOl], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(c~-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1, 1 -bis(S-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-S-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
l.S. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sul~lde, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanarate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, - 13- 2~27~
dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. AcYlaminophenols, for example lauric acid 4-hydroxyanilide, stearic acid 4-hydroxyanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.7. Esters of ~-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalarnide.
1.8. Esters of ~-(5-tert-butvl-4-hydroxy-3-methylphenYl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.
1.9. Esters of ~-(3~5-dicyclohexYI-4-hydroxvphenYl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenYl)propionic acid, for exarnple N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and li~ht stabilisers 2.1. 2-(2'-HydroxYphenyl~benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(a,a-dimethylbenzyl) derivative.
2.2. 2-Hvdroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 2~ 3 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and - 2'-hydroxy-4,4'-dirnethoxy derivative.
2.3~ Es_ers of substituted or unsubstituted benzoic acids. for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoykesorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-,~,~-diphenylacrylate, isooctyl a-cyano-~,~-diphenylacrylate, methyl a-carbomethoxycinnamate~ methyl a-cyano-~-methyl-p-methoxycinnamate, butyl a-cyano-~-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(,~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis~4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6~6-tetramethylpiperidyl) sebacate, bis(1,2,2,6,~pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediarnine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'-(~,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone).
2.7. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2~-dioctyloxy-S,S'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and its mixture with 20~2~
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy-disubstituted oxanilides, and o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hvdroxvphenyl)-1.3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-tlia~-ine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,~-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl aL~yl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro~S.S]undecane.
S. Compounds which destroY peroxides, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc sal~ of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto)propionate.
fi. PolYamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. B_sic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiarnide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, ~or example calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate and ~0~7~
potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
8. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcin~ a~ents, for example calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flameproofing agents, antistatic agents and blowing agents.
Of these costabilisers, the phenolic antioxidants, in particular benzyl compounds and the esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, have proven particularly advantageous, in particular 1,3,5-tris(3,~-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate (calcium salt) or an ester of ,I~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono, di- or tetrahydric alcohols, in particular with octadecanol, 1,6-hexanediol, pentaerythritol, thiodiethylene glycol or triethylene glycol.
Further preferred costabilisers are esters of thiodipropionic acid, for example lauryl thiodipropionate, stearyl thiodipropionate, myristyl thiodipropionate and tridecyl thiodipropionate.
The polyolefins which can be stabilised accoriding to the invention are preferably polymers of mono- or diolefins, such as polypropylene, polyisobutylene, polybutene, polyisoprene, polybutadiene and polyethylene, for example high- and low-density polyethylene (HDPE and LDPE) and linear low-density polyethylene (LLDPE). The stabilisation according to the invention of mixtures of these polymers is also possible.
Preferably, polyethylene and polypropylene are stabilised.
Incorporation of the compounds of the formulae (1) to (14) and, if appropriate, further costabilisers into the polymeric organic material is carried out by known methods, for example before or during moulding or else by applying the dissolved or disperse - 17 2~2~
compounds to the polymeric organic matelial, if necesary with subsequent evaporation of the solvent. The compounds can also be added to the materials to be stabilised in the forn of a masterbatch which contains these compounds, for example, in a concentration of 2.5 to 25 % by weight.
Thc compounds of the formulae (1) to (14) can also be added before or during polymerisation or before crosslinking.
The compounds can be incorporated into the material to be stabilised in pure form or encapsulated in waxes, oils or polymers.
The compounds can also be sprayed onto the polymer to be stabilised. They are capable of diluting other additives (for example the abovementioned customary additives) or melts ~hereof, making it possible to spray them onto the polymer to be stabilised also together with these additives. It is particularly advantageous to add them by spraying during deactivation of the polymerisation catalysts, it being possible, for example, to use the vapour used for deactivation for spraying.
In the case of spherically polymerised polyole~ms, it may be, for example, advantageous to apply the compounds, if appropriate together with other additives, by spraying.
Accordingly, a preferred embodiment of the present invention is the use of the compounds of the formulae (1) to (14) for the stabilisation of polyole~ms against oxidative, thermal or actinic degradation, these compounds being sprayed onto the polymer.
The materials thus stabilised can be used in various forms, for example as films, fibres, tapes, moulding materials, profiles or as binders for paints, adhesives or cements.
The examples which follow illustrate the invention further. Parts and percentages are by weight.
Example 1: Stabilisation of high-density polyethylene.
100 parts of high-molecular-weight polyethylene powder, prepared using chromium-containing catalysts, of melt index 1.7-2.3 (at l90GC/21.6 kg)~ are mixed with 0.05 part of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the stabiliser combination in the concentrations given in Table 1, and the mixture is ~,~6~7~
kneaded in a Brabender plastograph at 220C and 50 revolutions per minute. During this time, the resistance to kneading is continuously registered as torque. During the course of kneading, the polymer, after remaining constant for a fairly long time, starts to crosslink, which can be detected by the rapid increase in torque. In Table 1, the time until the torque increases noticeably is listed as the measure of stabiliser effect.
7 ~
Table 1:
.. _ ._ .__ .... ~
Experi- Stabiliser mixture (ppm)Increase in ment Benzofuran- Phosphorustorque after 2-one of the compound of the forrnula forrnula mmutes 11000 (15) 0 7.5 2 500 0 5.5 3 O 2000 (16) 20.0 4 0 1000 12.0 950 15.0 6 100 900 20.0 7 50 450 8.0 8 100 400 7.0 9 0 1000 (17) 18.0 950 43.0 11 50 450 33.0 12 100 900 44.0 13 0 500 11.0 14 50 450 21.0 100 400 21.0 16 50 200 6.0 17 0 1000 (18) 12.0 18 50 950 20.0 19 100 900 20.0 0 500 6.0 21 50 450 12.0 22 100 400 12.0 23 0 1000 (19) 30.0 24 50 950 52.0 100 900 60.0 26 0 500 12.0 27 50 450 26.0 28 100 400 33.0 29 0 1000 (20) 18.0 950 57.0 31 100 900 >60.0 32 0 500 14.0 33 50 450 28.0 34 100 400 32.0 7 ~
Table 1: (Continuation) -- ____ Experi- Stabiliser mixture (ppm) ment Benzofuran-2-one Phosphorus Lncrease m torque of the formula compound of the after minutes ormula _ . _ o (24)500 (21) 10.0 91 0 1000 16.0 92 50 950 35.0 93 0 500 (22) 8.0 g4 O 1000 12.0 95 100 (23)900 15.0 96 50 (26)450 (17) 22.5 97 100 (27)400 (19) 35.0 98 50 (25)950 (16) 15.5 99 50 (28)450 (20) 26.0 2060~7 ~
Benzofuran-2-one of the fo~nula 0-~
(15) ~3 Phosphorus compounds of the forrnula (16) ~ 3 (17) ~P~t~
C4Hg O P O
(18) (19) LC~o_p/~
2 ~
(20) (21) [ ~O ~ P-OC2H5 O - -- P O
(22) Benzofuran-2-ones of the formula CH3 ~
(23) H2sCIz -HC ~3 0~
~24) ~ ~ OCH3 206~7~
o - ~o (25) ~3 O ~ ~ O
(26) ~
~' O
P
(27) ~3~
O
~"~
(~8) +
e3~
o~o ~ = t-butyl 2~6~2~
Example 2: Stabilisation of polypropylene 1.3 kg of polypropylene powder (melt index: 3.2 g/10 min, measured at 230C/2.16 kg, titanium content greater than 40 ppm) are mixed with 0.05 % of calcium stearate, 0.05 %
of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and 0.05 % of the stabiliser mixture listed in Table 2. This mixture is extruded in an extruder having a cylinder diameter of 20 mm and a length of 400 mm at 100 revolutions per minute, the 3 heating zones being set to 260C, 270C and 280C. For cooling, the extrudate is let through a water bath and then granulated. The granules ob~ained are further extruded.
After each of 5 extrusions, the melt index is measured at 230C/2.16 kg. Furthermore, the yellowness index (YI) of platelets 2 mm in thickness prepared from the granules is determined by ASTM D 1925. The results are listed in Table 2. High values denote strong yellowing.
Table 2 Stabiliser mixture Melt index after YI after Expen-(ppm) 1st 2nd 3rd 4th 5th 1st 3rd 5th ment(16) (15) extrusion extrusion 351000 0 5.2 6.1 6.7 9.3 11.1 2.7 3.9 5.4 36 600 50 4.7 5.8 6.8 8.0 9.4 2.2 3.1 3.7 37 450 50 4.8 5.9 7.4 8.9 10.5 2.3 3.1 3.8 38 0 500 4.9 5.8 6.6 7.3 8.1 2.6 3.8 4.8 39 o 250 5.2 6.2 6.8 8.1 9.2 2.7 3.8 4.8 0 150 5.2 6.4 7.6 9.2 11.0 2.6 3.6 4.5 41 0 100 5.8 7.2 9.1 11.3 14.3 ~-? 3-9 4.7 ~6~2~3 Example 3: Example 2 is repeated, except that a mixture of the benzofuran-2-one of ~he formula ~15) and the phosphorus compound of the formula (17), (18) or (20) is used as the stabiliser. The results are summarised in Table 3.
T~ble 3 _ . Stabiliser mixture (ppm) Melt index after YI after Experl- Phosphorus Benzofuran- 1st 2nd 3rd 4th 5th 1st 2nd 3rd ment compound of 2-one of the .
the forrnula formula (15) extrus1on extrus1on 42 300 (17) 0 4.4 5.5 6.99.7 13.8 2.1 3.1 4.1 43 200 25 4.1 4.6 6.28.1 11.9 1.7 2.5 4.4 44 200 50 4.2 5.0 6.07.7 9.9 2.2 2.7 3.4 100 50 4.5 5.8 8.210.313.3 2.2 3.2 3.9 46 300 (20) 0 4.7 5.7 6.~8.3 10.1 2.0 3.0 3.6 47 200 25 4.6 5.5 6.67.9 9.8 1.9 2.5 2.8 48 200 50 4.4 5.1 5.97.6 9.0 1.8 2.5 3.2 49 100 50 4.8 6.0 7.49.3 11.6 1.9 2.5 3.1 500 (18) 0 4.9 6.2 7.910.112.8 2.6 3.9 4.4 51 340 25 4.8 6.0 7.38.3 10.2 2.4 3.0 4;2 52 340 50 4.3 5.2 6.17.2 8.6 2.3 3.4 3.9 53 180 50 4.6 5.7 7.29.0 11.2 2.3 3.1 3.6 7 ~
Example 4: Example 3 is repeated, except that the heating zones in the extruder are set to 240C, 250C and 260C. The results are summarised in Table 4.
.
Table 4 E:cpen- Stabiliser mixture (ppm) Melt index after YI a~ter ment Phosphorus Benzofuran- 1st3rd 5th 1st3rd 5th compound of 2-one of the the forrnula formula (15) extruslon extrusion 54S00 (16) 0 5.5 7.1 9.2 3.04.~ 5.4 551000 ~) 5.2 6.3 7.6 3.24.4 5.8 56675 25 4.8 6.0 7.1 2.94.2 5 3 _ .... -57300 (17) 0 4.8 6.310.4 2.~3.8 5.1 58200 25 5.7 7.210.3 2.83.7 4.6 59200 50 4.8 6.3 9.4 2.83.7 4 7 60100 50 6.3 ~.512.2 2.83.5 4.2 _ _ 61300 (20) 0 6.1 7.710.3 2.33.1 4.3 62200 25 5.9 7.4 9.5 2.13.0 3.8 63200 50 5.8 7.2 8.9 2.23.1 3 8 64100 50 6.3 8.010.6 2.22.9 3 7 .. _ . . . _ 500 (18) 5.9 7.4 9.4 3.14.5 5.~S
66 340 25 5.9 7.3 9.9 2.73.7 5 0 67 340 50 5.7 7.0 ~.7 2.9_ 3.8 46 - 27 - ~ 2 7 ~
Example 5: Example 3 is repeated, except tha~ a polypropylene is used which contains less than 3 ppm of titanium.
The results are summarised in Table 5.
Table S
.
Stabiliser mixture (ppm)Melt index after YI after Experi- Phosphorus Furan-2-one 1st 3rd 5th 3rd 5th ment compound of of the .
the formula forrnula (lS` extruslon extruslon 68 S00 (16) 0 3.7 6.6 11.2 3.0 3.5 691000 0 3.1 4.9 7.2 3.0 3.5 70 675 25 3.3 4.3 6.5 3.0 3.4 71 675 25 2.8 4.2 5.8 2.9 3.3 72 300 (17) 0 2.6 3.7 5.4 3.1 3.7 73 200 50 2.5 3.4 5.8 2.8 3.5 74 100 50 2.7 4.4 6.9 2.7 3.3 75 300 (20) 0 2.9 4.2 6.8 2.8 3.3 76 200 S0 2.5 3.4 5.3 2.7 3.4 77 1~0 50 2.6 4.0 6.3 2.7 3.3 78 S00 (18) 0 2.8 4-3 6.7 3.0 3.7 79 340 S0 2.5 3.4 5.0 3.1 3.2 80 180 S0 2.7 4.1 6.4 2.6 3.3
Stabilised polvole~m Tlle present invention relates to a polyolefin stabilised against thennal, oxidative andlor ` actinic degradation, which comprises a benzofuran-2-one and a phosphite or/and phosphonite as stabiliser.
.
The use of benzofuran-2-ones as stabilisers for polyolefins is described, for example, in US-A-4,32~,863 and US-A-4,338,244. According to these publications, these compounds are usually added to the polyole~ln in amounts of 0.01 to 5 %, relative to dle total weight of the material to be stabilised. Surprisingly, it has now been found that benzofuran-2-ones are also capable of effectively stabilising polyole~ms even in much lower concentrations if used together with phosphites, phosphonites or aza analogs thereof. In particular, this also effectively reduces the yellowing of the polyolefins during processing.
Accordingly, the present invention relates to a polyole~ln containing, as stabiliser, a mixture comprising at least one phosphite or phosphonite or aza analogs thereof and at least one benzofuran-2-one in an amount of 0.0001 to O.OlS % by weight of the formula Rs R3 ~ C = O
ill which Rl is phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine, R2 is hydrogen and R4 is hydrogen, alkyl having 1 tO 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenylalkyl having 1 to 12 carbon atoms in the alkyl moiety or chlorine, ~6~
R3 has the meaning of R2 or R4 or is a radical of the formula -(CH2~-OR6, O O O
-(CH23~-N(R7)2. ~cH2~-o-A-o-c~cH2 n~E, ~CH2~-NR8-A-NR8-C~CH2 n~E~ iCH2~C-NRg-A-O-(~CH2 n~E-~CH2~C--N N--c~CH2~ E, -CH2-S-R9, -CH(C6Hs)- ~OR6 or -D-E, in which R6 is hydrogen, aLlcyl having 1 to 18 carbon atoms, aLIcyl having 2 to 18 c~rbon atoms and interrupted by oxygen or sulfur, dialkylaminoaLkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, n is 0, 1 or 2, the substituents R7 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, a radical of the forrnula -C2H40H, ~C2H4~0~CmH2m~l or -C2H4-O-~-RIo or together with the nitrogen atom to which they are bound form a piperidine or morpholine radical, m is 1 to 18, Rlo is hydrogen, aLkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms, A is an alkylene having 2 to 22 carbon atoms, which may be interrupted by nitrogen, oxygen or sulfur, R8 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a ~otal of at most 16 carbon atoms, or benzyl, Rg is alkyl having 1 to 18 carbon atoms, D is -O-, -S-, -SO-, -SO2- or -C(Rll)2-, the substituents Rll are, independently of one another, hydrogen, alkyl having a total of at ` 20~(~2~3 .~
., O
most 16 carbon atoms, phenyl or a radical of the formula tCH~-OR6 or O
tCH2~-N(R7)2. or together with the carbon atom to which they are bound form a cycloalkyl having 5 to 7 carbon atoms, in which n, R6 and R7 are as defined, E is a radical of the formula ~C/
/ \
R2 H Rl hl which Rl, R2 and R4 are as defined, and Rs is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a O O
radical of the formula -CH2-~-OR6 or -CH2- ~-N(R7)2, in which R6 and R7 are as defined, or Rs together with R4 forms a tetramethylene radical.
The present invention also relates to a process for the stabilisation of polyolefins, which comprises incorporadng therein or applying thereto a stabiliser mixture as defined above.
The benzofuran-2-ones of the formula (1) and processes for their preparation are described in the mentioned IJS-A-4,325,863 and US-A-4,338,244. US-A-4,374,219; 4,318,845;
4,386,204; 4,409,346; 4,322,527; 4,661,594 and 4,407,976 have disclosed, for example, the phosphorus compounds of the formulae (2) to (14) and also processes for their preparation.
Alkyl substituents in the compounds of the formula (1) can contain up to 22 carbon atoms.
Exarnples of these are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl and the corresponding branched isomers, in particular tert-butyl, i-octyl and i-dodecyl. Alkoxy and alkoxycarbonyl radicals are derived from these groups as are the alkylene radicals which are contained in the definitions of the substituents shown in formula (1). The alkyl radicals : 2~2~
listed can be interrupted by oxygen or sulfur, in order to form in particular structural units such as -CH2CH2-O-CH2CH2-, -CH2CH2-S-CH2CH2- or -O-(CH2)6-O-. Alkyl radicals as substituents on the phenyl rings preferably occupy the 3 and 5 positions.
The compounds of the formula (1) are incorporated into the polyolefin in an amount of 0.0001 to 0.015 % by weight, relative to the total weight of the ma~erial to be stabilised, and preferably of 0.0001 to 0.012, in particular 0.0001 to 0.008, % by weight. Aparticularly preferred amount is the range from 0.0005 to 0.007, in particular 0.0005 to 0.005, % by weight.
~, Suitable substituents for the phosphorus compounds of the formulae (2) to (14) are, inter alia, alkyl radicals having up to 20 carbon atoms. These radicals and those alkyl groups which are intermpted by sulfur, oxygen or nitrogen-containing groups correspond to the alkyl substituents already mentioned. Examples of cycloalkyl radicals containing 5 to 8 carbon atoms are cyclopentyl, cyclohexyl and cyclooctyl.
Polyolefins according to the invention preferably contain 0.01 to 2, in paIticular 0.01 to 1, % by weight, relative to the total weight of the material to be stabilised, of phosphite or phosphonite or aza analog thereof, preferably one or more compounds of the formulae (2) to (14).
R3 is preferably hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula tCH2~-OR6 ~ tCH23~-N(R7)2 or -D-E~
in which n, R6, R7, D and E are as defined. R6 is preferably hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.
In A further group of preferably used benzofuran-2-ones, Rl is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms. R2 is hydrogen and R4 is hydrogen or alkyl having 1 to 12 carbon atoms, R3 is hydrogen, alkyl O O
having 1 to 12 carbon atoms, tCH2~C-OR6, tCH2~-N(R7)2 or -D-E, Rs is hydrogen, aL~cyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, -CH2-C-OR6 or 2 ~ 7 $
,. 5 .
-CH2-~-N(R7)2, or Rs together with R4 is tetramethylene, and n, R6, R7, D and E are as defined. Of these, preference is given to those compounds of the folmula (1) in which Rl is phenyl, R3 is hydrogen, aLl~yl having 1 to 12 carbon atoms or -D-E, R2 is hydrogen and R4 is hydrogen or alkyl having 1 to 4 carbon atoms, and Rs is aLlcyl having 1 to 20 carbon atoms, cyclopentyl or cyclohexyl, D and E being as def1ned, and in particular to those compounds in which Rl is phenyl, R3 is aLl~yl having 1 to 4 carbon atoms or -D-E, R2 and R4 are hydrogen, and Rs is aL~cyl having 1 to 4 carbon atoms or cyclopentyl or cyclohexyl, I) being -C(Rli)2- and E being a radical of the formula ~ \C o ~f /c\
in which the substituents Rl 1 are identical to or different from one another and are each allyl having 1 to 4 carbon atoms, and Rl, R2, R4 and Rs are as de~med.
The phosphites to be used according to the invention or aza analogs thereof preferably have the formula ~OR2 ~OR2 (2) RiO-P~ , (3) A - ~) p\
OR3 OR3 n' (4) (R~lo)m~-p(NR7Rs)3-m~ (5) A ~O-P(NR 7R 8)2) D~o/ 1~ ~ (7) ~ P--O~ A' 2~6~27~
H C>CO\ R' H C>~
H3C / ~R'11 H3C d (10) R'l3--X--P ~)C P--X-R'l3 or ` O O
R~
~ /f~R'14\
(11)W~
in which R'l, R'2 and R'3, independently of one another, are aLkyl having 1 to 18 carbon atoms, allyl having 1 to 18 carbon atoms which is substituted by halogen, -COOR'4, -CN or -CONR'4R'4, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR'4-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms, 2,2,6,6-tetramethylpiperid-4-yl, N-allyl- or N-benzyl- or N-alkyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety or N-alkanoyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety, or N-alkylene-2,2,6,6-tetramethylpiperidyl or N-alkylene-4-alkoxy-2,2,6,6-tetramethyl-piperidyl having 1 to 3 carbon atoms in the alkylene moiety and 1 to 18 carbon atoms in the alkoxy moiety, R'4 or the radicals R'4 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms orphenylalkyl ha-ving 1 to 4 carbon atoms in the alkyl moiety, n'is2,30r4, A' is alkylene having 2 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or -NR'4-, in which R'4 is as defined, or a radical af the formula 2~2~
., R's R~5 ~~ or {}B {~
,. R'6 R'6 if n'is2, A' is a radical of the formula ~C~H2r l- or N(C~H2CH2~, in which r is 5 or 6, if n' is 3, A' is the radical of the formula C(CH2~, if n' is 4, R's and R'6, independently of one another, are hydrogen or alkyl having 1 to 8 carbon ~toms, A" has the meaning of A', if n' is 2, B is a radical of the formula -CH2-, -CHR'4-, -(:IR~lR'4-, -S- or a direct ~ond, in which R' and R'4 are as defined, m' is 1 or 2, R'7 and R'8, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'7 or R'8 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-, p is 1 or 2, D' is methyl, if p is 1, and is -CH20CH2-, if p is 2, R'9 is methyl and R'lo has the meaning of R'l, qis20r3, R'll and R'l2, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R' ~md R'l2 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-0-CH2CH2-, or R'll is a radical of the formula / ~ CH3 --E'- Y1--P~
o / C~13 in which E' is alkylene having 2 to 18 carbon atoms or alkylene having 2 to 18 carbon atoms and interrupted by -S-, -0- or -NR',2-, in which R',2 is as defined, X and Yl, independently of one another, are -0- or -NR'12-, in which R'12 is as de~med, 2 ~ ~
R'13, when X is -O-, has the meani~g of R'l, and R'13, when X is -NR'12-, has the meanin5 of R'12, y is 1, 2 or 3, W is alkyl having 1 to 18 carbon atoms, a radical of the formula -OR'I6, -NR'17R'18 or fluorine, if y is 1, W is a radical of the formula -O-A"-O-, -NR'17-A"'-NR',7-, -O-A"'-NR'17- or H ~CyCH3 --O~<N--CH2--CH--Rlg~
if yis2, W is a radical of the formula R4C~CH20~, N(C2H40~ or N(C3H60~, in which R'4 is as defined, if y is 3, R'l6 has the meaning of R l.
R'l7 and R',8, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,~,6-pentamethylpiperid-4-yl radical, or R'17 and R'lg together form butylene, pentylene, hexylene or the radical of ~e fonnula -CH2C~12-O-C~H2CH2-~A" is as defined, A"' is alkylene having 2 to 12 carbon atoms or aLkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or NR'4-, in which R'4 is as defined, R'lg is hydrogen or methyl, the substituents R'l4 are, independently of one another, hydrogen, aLIcyl having 1 to 9 carbon stoms or cyclohexyl, R'l5 is hydrogen or methyl and Z is a direct bond, -~EI2-, -C(R'I4)2- or -S-, in which the substituents R~l4 are identical or different and are as deflned.
Particularly suitable phosphites have the formula (2), (3), (6), (B), (10) or (11).
Preferred phosphites of the formula (2) are those in which R'l, R'2 and R'3, independently of one another7 are alkyl having 1 to 18 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or 2,2,6,6-tetramethylpiperid-4-yl, in particular phenyl which is substituted, independently of ?,G6027~
. .
~ one another by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
.,~
In phosphites of the formula (3), A' is preferably alkylene having 2 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms, -CH2CH2-O-CH2CH2-, -CH2OEI2-O-CH2CH20-CH2CH2- or -CH2CH2-NR'~-CH2CH2-, if n' is 2, or A' is N(CH2CH2~, in which R'4 is alkyl having 1 to 4 carbon atoms, if n' is 3.
Phosphites of the formula (6) are preferred, if p is 1, D' is methyl, R'g is methyl and R'lo is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms.
Particularly suitable phosphites of the formula t8) are those in which R'~l and R'~2, independently of one another, are a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R'll is a radical of the formula / ~ CH3 --E'--N--P ~<CH3 ' in which E' is aLtcylene having 2 to 6 carbon atoms and R'l2 is as defined.
P~rticularly suitable phosphites of the formula (10) are those in which R'13-X- is a radical of the formula -N(~',2)2 or phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, in which the substituents R'12 are, independently of one ,another, alkyl having 1 to 12 carbon atoms or a 2,2,6,6-tetra- or 1,'~,2,6,6-pentamethylpiperid-4-yl radical, in particular in which R'13-~- is phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
Preferably, phosphites of the formula (11) are used in which W is a radical of the forrnula -OR'16, -NR'l7R'l8 or fluorine, if y is 1, or W is a radical of the formula -O-CH2CH2-NR'4-CH2CH2-O-, if y is 2, or W is a radical of the fonnula N(CH2CH20~, if y is 3, in which R'l6 is alkyl having 1 to 18 carbon atoms, R' ~7 and R'l8, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'l7 and R'l8 together forrn a piperidyl, morpholinyl or hexamethyleneimino radical, and R'4 is as defined, Z is a direct bond, -CH2- or -CHCH3-, and the two substituents R'14 are, independently of one another, alkyl having 1 to 4 carbon atoms, and in particular those in which W is 2-ethylhexoxy or fluorine, R'14 is tert-butyl, R'ls is hydrogen and ~ is -CH2- or -CH(CH3)-, if y is 1, or W is a radical of the formula -O-CH2CH2-NCH3-CH2CH2-O-, if y is 2.
Suitable phosphonites or aza analogs thereof are preferably those of the formulae (12) Hsc6-p(oR2o)s(NR2lR22)2-s~
/ R24~
(13) ~ R25 G f t Kand \~4~O /
R24 k (14) R21~0 ~ p~O~R~227 in which R20 is alkyl having 1 to 20 carbon atoms, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR26-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or is 2,2,6,6-tetramethylpiperid-4-yl, R26 is alkyl having 1 to 4 carbon atoms, and R2l and R22, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R21 and R22 together forrn butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2-CH2-.
s is 1 or 2, the substituents R24 are, independently of one another, hydrogen, alkyl having 1 to 12 carbon atoms or cyclohexyl, 2 ~ 7 ~
:`
R25 is hydrogen or methyl, G is a direct bond, -CH2-, -C(R24)2- or -S-, in which the substituents R24 are identical or different and are as defined, k is 1 or 2, K is phenyl or naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, if k is 1, or K is phenylene or biphenylene, if k is 2, R27 and R28, independently of one another, are phenyl, naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms and in particular those of the formula (12) in which R20 is alkyl having 1 to 20 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, and R2l and R22, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl or cyclohexyl, or R21 and R22 together form pentylene, hexylene or the radical of the formula -CH2CH2-O-C~2CH2-. Particularly preferred are compounds in which R20 is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
Particularly suitable phosphonites of the foimula (13) are those in which the substituents R24 are, independently of one another, alkyl having 1 to 12 carbon atoms, G is a direct bond or -CH2- and k is 1.
In preferred phosphonites of the formula (14), R27 and R28 are, independently of one another, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 8 carbon atoms.
Furthermore, it has been shown that in certain cases the additional use of at least one costabiliser, in particular a phenolic antioxidant, can have advantageous effects. Examples are:
1. Antioxidants 1.1. Alkvlated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(c~-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, ~6~2~
.
; -12-2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.
1.2. Alkvlated hvdro~uinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.
1.3. Hvdroxylated thiodiphenvl ethers, for exarnple 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis~4-octylphenol), 4,4'-thiobis(6-~ert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2 '-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenOl], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(c~-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1, 1 -bis(S-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-S-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
l.S. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sul~lde, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanarate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, - 13- 2~27~
dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. AcYlaminophenols, for example lauric acid 4-hydroxyanilide, stearic acid 4-hydroxyanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.7. Esters of ~-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalarnide.
1.8. Esters of ~-(5-tert-butvl-4-hydroxy-3-methylphenYl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.
1.9. Esters of ~-(3~5-dicyclohexYI-4-hydroxvphenYl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenYl)propionic acid, for exarnple N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and li~ht stabilisers 2.1. 2-(2'-HydroxYphenyl~benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(a,a-dimethylbenzyl) derivative.
2.2. 2-Hvdroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 2~ 3 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and - 2'-hydroxy-4,4'-dirnethoxy derivative.
2.3~ Es_ers of substituted or unsubstituted benzoic acids. for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoykesorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-,~,~-diphenylacrylate, isooctyl a-cyano-~,~-diphenylacrylate, methyl a-carbomethoxycinnamate~ methyl a-cyano-~-methyl-p-methoxycinnamate, butyl a-cyano-~-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(,~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis~4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6~6-tetramethylpiperidyl) sebacate, bis(1,2,2,6,~pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediarnine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'-(~,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone).
2.7. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2~-dioctyloxy-S,S'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and its mixture with 20~2~
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy-disubstituted oxanilides, and o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hvdroxvphenyl)-1.3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-tlia~-ine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,~-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl aL~yl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro~S.S]undecane.
S. Compounds which destroY peroxides, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc sal~ of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto)propionate.
fi. PolYamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. B_sic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiarnide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, ~or example calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate and ~0~7~
potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
8. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcin~ a~ents, for example calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flameproofing agents, antistatic agents and blowing agents.
Of these costabilisers, the phenolic antioxidants, in particular benzyl compounds and the esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, have proven particularly advantageous, in particular 1,3,5-tris(3,~-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate (calcium salt) or an ester of ,I~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono, di- or tetrahydric alcohols, in particular with octadecanol, 1,6-hexanediol, pentaerythritol, thiodiethylene glycol or triethylene glycol.
Further preferred costabilisers are esters of thiodipropionic acid, for example lauryl thiodipropionate, stearyl thiodipropionate, myristyl thiodipropionate and tridecyl thiodipropionate.
The polyolefins which can be stabilised accoriding to the invention are preferably polymers of mono- or diolefins, such as polypropylene, polyisobutylene, polybutene, polyisoprene, polybutadiene and polyethylene, for example high- and low-density polyethylene (HDPE and LDPE) and linear low-density polyethylene (LLDPE). The stabilisation according to the invention of mixtures of these polymers is also possible.
Preferably, polyethylene and polypropylene are stabilised.
Incorporation of the compounds of the formulae (1) to (14) and, if appropriate, further costabilisers into the polymeric organic material is carried out by known methods, for example before or during moulding or else by applying the dissolved or disperse - 17 2~2~
compounds to the polymeric organic matelial, if necesary with subsequent evaporation of the solvent. The compounds can also be added to the materials to be stabilised in the forn of a masterbatch which contains these compounds, for example, in a concentration of 2.5 to 25 % by weight.
Thc compounds of the formulae (1) to (14) can also be added before or during polymerisation or before crosslinking.
The compounds can be incorporated into the material to be stabilised in pure form or encapsulated in waxes, oils or polymers.
The compounds can also be sprayed onto the polymer to be stabilised. They are capable of diluting other additives (for example the abovementioned customary additives) or melts ~hereof, making it possible to spray them onto the polymer to be stabilised also together with these additives. It is particularly advantageous to add them by spraying during deactivation of the polymerisation catalysts, it being possible, for example, to use the vapour used for deactivation for spraying.
In the case of spherically polymerised polyole~ms, it may be, for example, advantageous to apply the compounds, if appropriate together with other additives, by spraying.
Accordingly, a preferred embodiment of the present invention is the use of the compounds of the formulae (1) to (14) for the stabilisation of polyole~ms against oxidative, thermal or actinic degradation, these compounds being sprayed onto the polymer.
The materials thus stabilised can be used in various forms, for example as films, fibres, tapes, moulding materials, profiles or as binders for paints, adhesives or cements.
The examples which follow illustrate the invention further. Parts and percentages are by weight.
Example 1: Stabilisation of high-density polyethylene.
100 parts of high-molecular-weight polyethylene powder, prepared using chromium-containing catalysts, of melt index 1.7-2.3 (at l90GC/21.6 kg)~ are mixed with 0.05 part of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the stabiliser combination in the concentrations given in Table 1, and the mixture is ~,~6~7~
kneaded in a Brabender plastograph at 220C and 50 revolutions per minute. During this time, the resistance to kneading is continuously registered as torque. During the course of kneading, the polymer, after remaining constant for a fairly long time, starts to crosslink, which can be detected by the rapid increase in torque. In Table 1, the time until the torque increases noticeably is listed as the measure of stabiliser effect.
7 ~
Table 1:
.. _ ._ .__ .... ~
Experi- Stabiliser mixture (ppm)Increase in ment Benzofuran- Phosphorustorque after 2-one of the compound of the forrnula forrnula mmutes 11000 (15) 0 7.5 2 500 0 5.5 3 O 2000 (16) 20.0 4 0 1000 12.0 950 15.0 6 100 900 20.0 7 50 450 8.0 8 100 400 7.0 9 0 1000 (17) 18.0 950 43.0 11 50 450 33.0 12 100 900 44.0 13 0 500 11.0 14 50 450 21.0 100 400 21.0 16 50 200 6.0 17 0 1000 (18) 12.0 18 50 950 20.0 19 100 900 20.0 0 500 6.0 21 50 450 12.0 22 100 400 12.0 23 0 1000 (19) 30.0 24 50 950 52.0 100 900 60.0 26 0 500 12.0 27 50 450 26.0 28 100 400 33.0 29 0 1000 (20) 18.0 950 57.0 31 100 900 >60.0 32 0 500 14.0 33 50 450 28.0 34 100 400 32.0 7 ~
Table 1: (Continuation) -- ____ Experi- Stabiliser mixture (ppm) ment Benzofuran-2-one Phosphorus Lncrease m torque of the formula compound of the after minutes ormula _ . _ o (24)500 (21) 10.0 91 0 1000 16.0 92 50 950 35.0 93 0 500 (22) 8.0 g4 O 1000 12.0 95 100 (23)900 15.0 96 50 (26)450 (17) 22.5 97 100 (27)400 (19) 35.0 98 50 (25)950 (16) 15.5 99 50 (28)450 (20) 26.0 2060~7 ~
Benzofuran-2-one of the fo~nula 0-~
(15) ~3 Phosphorus compounds of the forrnula (16) ~ 3 (17) ~P~t~
C4Hg O P O
(18) (19) LC~o_p/~
2 ~
(20) (21) [ ~O ~ P-OC2H5 O - -- P O
(22) Benzofuran-2-ones of the formula CH3 ~
(23) H2sCIz -HC ~3 0~
~24) ~ ~ OCH3 206~7~
o - ~o (25) ~3 O ~ ~ O
(26) ~
~' O
P
(27) ~3~
O
~"~
(~8) +
e3~
o~o ~ = t-butyl 2~6~2~
Example 2: Stabilisation of polypropylene 1.3 kg of polypropylene powder (melt index: 3.2 g/10 min, measured at 230C/2.16 kg, titanium content greater than 40 ppm) are mixed with 0.05 % of calcium stearate, 0.05 %
of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and 0.05 % of the stabiliser mixture listed in Table 2. This mixture is extruded in an extruder having a cylinder diameter of 20 mm and a length of 400 mm at 100 revolutions per minute, the 3 heating zones being set to 260C, 270C and 280C. For cooling, the extrudate is let through a water bath and then granulated. The granules ob~ained are further extruded.
After each of 5 extrusions, the melt index is measured at 230C/2.16 kg. Furthermore, the yellowness index (YI) of platelets 2 mm in thickness prepared from the granules is determined by ASTM D 1925. The results are listed in Table 2. High values denote strong yellowing.
Table 2 Stabiliser mixture Melt index after YI after Expen-(ppm) 1st 2nd 3rd 4th 5th 1st 3rd 5th ment(16) (15) extrusion extrusion 351000 0 5.2 6.1 6.7 9.3 11.1 2.7 3.9 5.4 36 600 50 4.7 5.8 6.8 8.0 9.4 2.2 3.1 3.7 37 450 50 4.8 5.9 7.4 8.9 10.5 2.3 3.1 3.8 38 0 500 4.9 5.8 6.6 7.3 8.1 2.6 3.8 4.8 39 o 250 5.2 6.2 6.8 8.1 9.2 2.7 3.8 4.8 0 150 5.2 6.4 7.6 9.2 11.0 2.6 3.6 4.5 41 0 100 5.8 7.2 9.1 11.3 14.3 ~-? 3-9 4.7 ~6~2~3 Example 3: Example 2 is repeated, except that a mixture of the benzofuran-2-one of ~he formula ~15) and the phosphorus compound of the formula (17), (18) or (20) is used as the stabiliser. The results are summarised in Table 3.
T~ble 3 _ . Stabiliser mixture (ppm) Melt index after YI after Experl- Phosphorus Benzofuran- 1st 2nd 3rd 4th 5th 1st 2nd 3rd ment compound of 2-one of the .
the forrnula formula (15) extrus1on extrus1on 42 300 (17) 0 4.4 5.5 6.99.7 13.8 2.1 3.1 4.1 43 200 25 4.1 4.6 6.28.1 11.9 1.7 2.5 4.4 44 200 50 4.2 5.0 6.07.7 9.9 2.2 2.7 3.4 100 50 4.5 5.8 8.210.313.3 2.2 3.2 3.9 46 300 (20) 0 4.7 5.7 6.~8.3 10.1 2.0 3.0 3.6 47 200 25 4.6 5.5 6.67.9 9.8 1.9 2.5 2.8 48 200 50 4.4 5.1 5.97.6 9.0 1.8 2.5 3.2 49 100 50 4.8 6.0 7.49.3 11.6 1.9 2.5 3.1 500 (18) 0 4.9 6.2 7.910.112.8 2.6 3.9 4.4 51 340 25 4.8 6.0 7.38.3 10.2 2.4 3.0 4;2 52 340 50 4.3 5.2 6.17.2 8.6 2.3 3.4 3.9 53 180 50 4.6 5.7 7.29.0 11.2 2.3 3.1 3.6 7 ~
Example 4: Example 3 is repeated, except that the heating zones in the extruder are set to 240C, 250C and 260C. The results are summarised in Table 4.
.
Table 4 E:cpen- Stabiliser mixture (ppm) Melt index after YI a~ter ment Phosphorus Benzofuran- 1st3rd 5th 1st3rd 5th compound of 2-one of the the forrnula formula (15) extruslon extrusion 54S00 (16) 0 5.5 7.1 9.2 3.04.~ 5.4 551000 ~) 5.2 6.3 7.6 3.24.4 5.8 56675 25 4.8 6.0 7.1 2.94.2 5 3 _ .... -57300 (17) 0 4.8 6.310.4 2.~3.8 5.1 58200 25 5.7 7.210.3 2.83.7 4.6 59200 50 4.8 6.3 9.4 2.83.7 4 7 60100 50 6.3 ~.512.2 2.83.5 4.2 _ _ 61300 (20) 0 6.1 7.710.3 2.33.1 4.3 62200 25 5.9 7.4 9.5 2.13.0 3.8 63200 50 5.8 7.2 8.9 2.23.1 3 8 64100 50 6.3 8.010.6 2.22.9 3 7 .. _ . . . _ 500 (18) 5.9 7.4 9.4 3.14.5 5.~S
66 340 25 5.9 7.3 9.9 2.73.7 5 0 67 340 50 5.7 7.0 ~.7 2.9_ 3.8 46 - 27 - ~ 2 7 ~
Example 5: Example 3 is repeated, except tha~ a polypropylene is used which contains less than 3 ppm of titanium.
The results are summarised in Table 5.
Table S
.
Stabiliser mixture (ppm)Melt index after YI after Experi- Phosphorus Furan-2-one 1st 3rd 5th 3rd 5th ment compound of of the .
the formula forrnula (lS` extruslon extruslon 68 S00 (16) 0 3.7 6.6 11.2 3.0 3.5 691000 0 3.1 4.9 7.2 3.0 3.5 70 675 25 3.3 4.3 6.5 3.0 3.4 71 675 25 2.8 4.2 5.8 2.9 3.3 72 300 (17) 0 2.6 3.7 5.4 3.1 3.7 73 200 50 2.5 3.4 5.8 2.8 3.5 74 100 50 2.7 4.4 6.9 2.7 3.3 75 300 (20) 0 2.9 4.2 6.8 2.8 3.3 76 200 S0 2.5 3.4 5.3 2.7 3.4 77 1~0 50 2.6 4.0 6.3 2.7 3.3 78 S00 (18) 0 2.8 4-3 6.7 3.0 3.7 79 340 S0 2.5 3.4 5.0 3.1 3.2 80 180 S0 2.7 4.1 6.4 2.6 3.3
Claims (30)
1. A polyolefin containing, as stabiliser, a mixture comprising at least one phosphite or phosphonite or aza analogs thereof and at least one benzofuran-2-one in an amount of 0.0001 to 0.015 % by weight of the formula (1) , in which R1 is phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine, R2 is hydrogen and R4 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenylalkyl having 1 to 12 carbon atoms in the alkyl moiety or chlorine, R3 has the meaning of R2 or R4 or is a radical of the formula , , .
, , , or -D-E, in which R6 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms and interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, n is 0, 1 or 2, the substituents R7 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, a radical of the formula -C2H4OH, -C2H4-O-CmH2m+1 or or together with the nitrogen atom to which they are bound form a piperidine or morpholine radical, m is 1 to 18, R10 is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms, A is an alkylene having 2 to 22 carbon atoms, which may be interrupted by nitrogen, oxygen or sulfur, R8 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, or benzyl, R9 is alkyl having 1 to 18 carbon atoms, D is-O-, -S-, -SO-, -SO2- or-C(R11)2-, the substituents R11 are, independently of one another, hydrogen, alkyl having a total of at most 16 carbon atoms, phenyl or a radical of the formula or , or together with the carbon atom to which they are bound form a cycloalkyl having 5 to 7 carbon atoms, in which n, R6 and R7 are as defined, E is a radical of the formula in which R1, R2 and R4 are as defined, and R5 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula or , in which R6 and R7 are as defined, or R5 together with R4 forms a tetramethylene radical.
, , , or -D-E, in which R6 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms and interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms, n is 0, 1 or 2, the substituents R7 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, a radical of the formula -C2H4OH, -C2H4-O-CmH2m+1 or or together with the nitrogen atom to which they are bound form a piperidine or morpholine radical, m is 1 to 18, R10 is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms, A is an alkylene having 2 to 22 carbon atoms, which may be interrupted by nitrogen, oxygen or sulfur, R8 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, or benzyl, R9 is alkyl having 1 to 18 carbon atoms, D is-O-, -S-, -SO-, -SO2- or-C(R11)2-, the substituents R11 are, independently of one another, hydrogen, alkyl having a total of at most 16 carbon atoms, phenyl or a radical of the formula or , or together with the carbon atom to which they are bound form a cycloalkyl having 5 to 7 carbon atoms, in which n, R6 and R7 are as defined, E is a radical of the formula in which R1, R2 and R4 are as defined, and R5 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula or , in which R6 and R7 are as defined, or R5 together with R4 forms a tetramethylene radical.
2. A polyolefin according to claim 1, wherein the benzofuran-2-one of the formula (1) is present in an amount of 0.0001 to 0.012 % by weight, in particular 0.0001 to 0.008 % by weight.
3. A polyolefin according to claim 1, wherein the phosphite or phosphonite or the aza analog thereof is present in an amount of 0.01 to 2 % by weight, in particular up to 1 % by weight.
4. A polyolefin according to claim 1, wherein R3 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula , or -D-E, in which n, R6, R7, D and E are as defined in claim 1.
5. A polyolefin according to claim 4, wherein R6 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.
6. A polyolefin according to claim 1, wherein R1 is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms, R2 is hydrogen, R4 is hydrogen or alkyl having 1 to 12 carbon atoms, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, , or -D-E, R5 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, or or R5 together with R4 forms a tetramethylene radical, in which n, R6, R7, D and E are as defined in claim 1.
7. A polyolefin according to claim 6, wherein R1 is phenyl, R3 is hydrogen, alkyl having 1 to 12 carbon atoms or -D-E, R4 is hydrogen or alkyl having 1 to 4 carbon atoms, and R5 is alkyl having 1 to 20 carbon atoms, cyclopentyl or cyclohexyl, D and E being as defined in claim 6.
8. A polyolefin according to claim 7, wherein R1 is phenyl, R3 is alkyl having 1 to 4 carbon atoms or -D-E, R2 and R4 are hydrogen, and R5 is alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being -C(R11)2- and E being a radical of the formula in which the substituents R11 are identical to or different from one another and are each alkyl having 1 to 4 carbon atoms and R1, R2, R4 and R5 are as defined.
9. A polyolefin according to claim 1, wherein the phosphite or the aza analog thereof has the formula (2) , (3) , (4) , (5) , (6) , (7) , (8) , (9) , (10) or (11) in which R'1, R'2 and R'3, independently of one another, are alkyl having 1 to 18 carbon atoms, alkyl having 1 to 18 carbon atoms which is substituted by halogen, -COOR'4, -CN or -CONR'4R'4, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR'4-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms, 2,2,6,6-tetramethylpiperid-4-yl, N-allyl- or N-benzyl- or N-alkyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety or N-alkanoyl-2,2,6,6-tetramethylpiperid-4-yl having 1 to 4 carbon atoms in the alkyl moiety, or N-alkylene-2,2,6,6-tetramethylpiperidyl or N-alkylene-4-alkoxy-2,2,6,6-tetramethyl-piperidyl having 1 to 3 carbon atoms in the alkylene moiety and 1 to 18 carbon atoms in the alkoxy moiety, R'4 or the radicals R'4 are, independently of one another, hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, n'is 2,3 or 4, A' is alkylene having 2 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or -NR'4-, in which R'4 is as defined, or a radical of the formula or if n'is 2, A' is a radical of the formula -C1H2r-1- or , in which r is 5 or 6, if n' is 3, A' is the radical of the formula , if n' is 4, R'5 and R'6, independently of one another, are hydrogen or alkyl having 1 to 8 carbon atoms, A" has the meaning of A', if n' is 2, B is a radical of the formula -CH2-, -CHR'4-, -CR'1R'4-, -S- or a direct bond, in which R'1 and R'4 are as defined, m' is 1 or 2, R'7 and R'8, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'7 or R'8 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-, p is 1 or 2, D' is methyl, if p is 1, and is -CH2OCH2-, if p is 2, R'9 is methyl and R'10 has the meaning of R'1, q is 2 or 3, R'11 and R'12, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R'11 and R'12 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-, or R'11 is a radical of the formula , in which E' is alkylene having 2 to 18 carbon atoms or alkylene having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR'12-, in which R'12 is as defined, X and Y1, independently of one another, are -O- or -NR'12-, in which R'12 is as defined, R'13, when X is -O-, has the meaning of R'1, and R'13, when x is -NR'12-, has the meaning of R'12, y is 1, 2 or 3, W is alkyl having 1 to 18 carbon atoms, a radical of the formula -OR'16, -NR'17R'18 or fluorine, if y is 1, W is a radical of the formula -O-A"-O-, -NR'17-A"'-NR'17-, -O-A"'-NR'17- or if y is 2, W is a radical of the formula , or , in which R'4 is as defined, if y is 3, R'16 has the meaning of R 1, R'17 and R'18, independently of one another, are allyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R'17 and R'18 together form butylene, pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-, A" is as defined, A"' is alkylene having 2 to 12 carbon atoms or alkylene having 2 to 12 carbon atoms and interrupted by -S-, -O- or -NR'4-, in which R'4 is as defined, R'19 is hydrogen or methyl, the substituents R'14 are, independently of one another, hydrogen, alkyl having 1 to 9 carbon atoms or cyclohexyl, R'15 is hydrogen or methyl and Z is a direct bond, -CH2-, -C(R'14)2- or -S-, in which the substituents R'14 are identical or different and are as defined.
10. A polyolefin according to claim 9, wherein the phosphite has the formula (2), (3), (6), (8), (10) or (11).
11. A polyolefin according to claim 9, wherein in the phosphite of the formula (2) R'1, R'2 and R'3 are, independently of one another, alkyl having 1 to 18 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or are 2,2,6,6-tetramethylpiperid-4-yl.
12. A polyolefin according to claim 11, wherein R'1, R'2 and R'3 are, independently of one another, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
13. A polyolefin according to claim 9, wherein in the phosphite of the formula (3) A' is alkylene having 2 to 12 carbon atoms, -CH2CH2-O-CH2CH2-.
-CH2CH2-O-CH2CH2O -CH2CH2- or -CH2CH2-NR'4-CH2CH2-, if n' is 2, or A' is n , in which R'4 is alkyl having 1 to 4 carbon atoms, if n' is 3.
-CH2CH2-O-CH2CH2O -CH2CH2- or -CH2CH2-NR'4-CH2CH2-, if n' is 2, or A' is n , in which R'4 is alkyl having 1 to 4 carbon atoms, if n' is 3.
14. A polyolefin according to claim 9, wherein in the phosphite of the formula (6) p is 1, D' is methyl, R'9 is methyl and R'10 is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms.
15. A polyolefin according to claim 9, wherein in the phosphite of the formula (8) R' and R'12 are, independently of one another, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R'11 is a radical of the formula in which E' is alkylene having 2 to 6 carbon atoms and R'12 is as defined.
16. A polyolefin according to claim 9, wherein in the phosphite of the formula (10) R'13-X- is a radical of the formula -N(R'12)2 or phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, in which the substituents R'12 are, independently of one another, alkyl having 1 to 12 carbon atoms or a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical.
17. A polyolefin according to claim 16, where R'13-X- is phenoxy which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
18. A polyolefin according to claim 9, wherein in the phosphite of the formula (11) W is a radical of the formula -OR'16, -NR'17R'18 or fluorine, if y is 1, or W is a radical of the formula -O-CH2CH2-NR'4-CH2CH2-O-, if y is 2, or W is a radical of the formula , if y is 3, in which R'16 is alkyl having 1 to 18 carbon atoms, R'17 and R'18, independently of one another, are alkyl having 1 to 18 carbon atoms, cyclohexyl or benzyl, or R'17 and R'18 together form a piperidyl, morpholinyl or hexamethyleneimino radical, and R'4 is as defined in claim 10, Z is a direct bond, -CH2- or -CHCH3-, and the two substituents R'14, are, independently of one another, alkyl having 1 to 4 carbon atoms.
19. A polyolefin according to claim 18, wherein W is 2-ethylhexoxy or fluorine, R'14 is tert-butyl, R'15 is hydrogen, and Z is -CH2- or -CH(CH3)-, if y is 1, or W is a radical of the formula -O-CH2CH2-NCH3-CH2CH2-O-, if y is 2.
20. A polyolefin according to claim 1, wherein the phosphonite or the aza analog thereof is of the formula (12) H5C6-P(OR20)s(NR21R22)2-s, (13) or (14) in which R20 is alkyl having 1 to 20 carbon atoms, alkyl having 2 to 18 carbon atoms and interrupted by -S-, -O- or -NR26-, cycloalkyl having 5 to 8 carbon atoms, phenyl or naphthyl, phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, or is 2,2,6,6-tetramethylpiperid-4-yl, R26 is alkyl having 1 to 4 carbon atoms, and R21 and R22 independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl, a 2,2,6,6-tetra- or 1,2,2,6,6-pentamethylpiperid-4-yl radical, or R21 and R22 together form butylene, pentylene, hexylene or the radical of the formula s is 1 or 2, the substituents R24 are, independently of one another, hydrogen, alkyl having 1 to 12 carbon atoms or cyclohexyl, R25 is hydrogen or methyl, G is a direct bond, -CH2-, -C(R24)2- or -S-, in which the substituents R24 are identical or different and are as defined, k is 1 or 2, K is phenyl or naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms, if k is 1, or K is phenylene or biphenylene, if k is 2, R27 and R28, independently of one another, are phenyl, naphthyl, or phenyl or naphthyl each of which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms.
21. A polyolefin according to claim 20, wherein in the phosphonite of the formula (12) R20 is alkyl having I to 20 carbon atoms, phenyl, phenyl which is substituted by 1 to 3 alkylene radicals having a total of 1 to 18 carbon atoms, and R21 and R22, independently of one another, are alkyl having 1 to 18 carbon atoms, benzyl or cyclohexyl, or R21 and R22 together form pentylene, hexylene or the radical of the formula -CH2CH2-O-CH2CH2-.
22. A polyolefin according to claim 21, wherein R20 is phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 12 carbon atoms.
23. A polyolefin according to claim 20, wherein in the phosphonite of the formula (13) the substituents R24 are, independently of one another, alkyl having 1 to 12 carbon atoms, (G is a direct bond or -CH2- and k is 1.
24. A polyolefin according to claim 20, wherein in the phosphonite of the formula (14) R27 and R28 are, independently of one another, phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 8 carbon atoms.
25. A polyolefin according to claim 1, which additionally contains at least one costabiliser, in particular a phenolic antioxidant.
26. A polyolefin according to claim 25, which contains as costabiliser 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphophonate (calcium salt) or an ester of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with octadecanol, 1,6-hexanediol, pentaerythritol, thiodiethylene glycol or triethylene glycol.
27. A polyolefin according to claim 1, wherein the polyolefin is polyethylene, polypropylene, polyisobutylene, polybutene, polyisoprene or polybutadiene or a mixture of these polymers.
28. A polyolefin according to claim 27, wherein the polyolefin is polyethylene or polypropylene.
29. A process for the stabilisation of polyolefins, which comprises incorporating therein or applying thereto a stabiliser mixture as defined in claim 1.
30. Use of a stabiliser mixture as defined in claim 1 for the stabilisation of polyolefins.
FD 43/KH/ms*/PM
FD 43/KH/ms*/PM
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH289/91-9 | 1991-01-31 | ||
| CH28991 | 1991-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2060276A1 true CA2060276A1 (en) | 1992-08-01 |
Family
ID=4183600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002060276A Abandoned CA2060276A1 (en) | 1991-01-31 | 1992-01-29 | Stabilised polyolefin |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0565371A (en) |
| CA (1) | CA2060276A1 (en) |
| DE (1) | DE4202276A1 (en) |
| FR (1) | FR2672292A1 (en) |
| GB (1) | GB2252325A (en) |
| IT (1) | IT1255635B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW206220B (en) * | 1991-07-01 | 1993-05-21 | Ciba Geigy Ag | |
| US5616636A (en) * | 1992-03-11 | 1997-04-01 | Sandoz Ltd. | Phosphonite-hals and phosphite-hals compounds as stabilizers |
| GB2265377B (en) * | 1992-03-11 | 1996-07-31 | Sandoz Ltd | The use of phosphonite-HALS and phosphite-HALS compounds for the stabilisation of polyolefins |
| TW260686B (en) * | 1992-05-22 | 1995-10-21 | Ciba Geigy | |
| GB2267490B (en) * | 1992-05-22 | 1995-08-09 | Ciba Geigy Ag | 3-(Carboxymethoxyphenyl)benzofuran-2-one stabilisers |
| NL9300801A (en) * | 1992-05-22 | 1993-12-16 | Ciba Geigy | 3- (ACYLOXYPHENYL) BENZOFURAN-2-ON AS STABILIZERS. |
| TW255902B (en) * | 1992-09-23 | 1995-09-01 | Ciba Geigy | |
| MX9305489A (en) * | 1992-09-23 | 1994-03-31 | Ciba Geigy Ag | 3- (DIHIDROBENZOFURAN-5-IL) BENZOFURAN-2-ONAS, STABILIZERS. |
| EP0608198A1 (en) * | 1993-01-18 | 1994-07-27 | Ciba-Geigy Ag | Cyclic diphenylacetonenitriles as stabilisers |
| CH686306A5 (en) | 1993-09-17 | 1996-02-29 | Ciba Geigy Ag | 3-aryl-benzofuranones as stabilizers. |
| TW270133B (en) * | 1993-09-17 | 1996-02-11 | Ciba Geigy | |
| JPH09506917A (en) * | 1993-12-22 | 1997-07-08 | チバ−ガイギー アクチエンゲゼルシャフト | Method for stabilizing a PVDC-containing polyolefin mixture and stabilizer mixture for a PVDC-containing polyolefin mixture |
| US6521681B1 (en) * | 1996-07-05 | 2003-02-18 | Ciba Specialty Chemicals Corporation | Phenol-free stabilization of polyolefin fibres |
| DE59702969D1 (en) * | 1996-10-30 | 2001-03-08 | Ciba Sc Holding Ag | Stabilizer combination for the rotomolding process |
| US5834541A (en) * | 1997-05-02 | 1998-11-10 | Montell North America Inc. | Olefin polymer composition having low smoke generation and fiber and film prepared therefrom |
| DE19730629C2 (en) * | 1997-07-17 | 2001-06-13 | Borealis Gmbh Schwechat Mannsw | Modified polymers containing methylene sequences, process for their preparation and use |
| GB2333296B (en) * | 1998-01-15 | 2000-09-27 | Ciba Sc Holding Ag | Stabilisers and anti-ozonants for elastomers |
| AU3331399A (en) * | 1998-03-24 | 1999-10-18 | Ciba Specialty Chemicals Holding Inc. | Stabilisation of organic materials |
| US6541549B2 (en) | 1999-11-01 | 2003-04-01 | Crompton Corporation | Non-xenoestrogenic stabilizers for organic materials |
| JP2003089734A (en) * | 2001-09-19 | 2003-03-28 | Sumitomo Seika Chem Co Ltd | Polypropylene resin composition |
| US20250145796A1 (en) * | 2021-10-22 | 2025-05-08 | Mitsubishi Gas Chemical Company, Inc. | Thermoplastic resin composition, molded article, and method for producing and method for improving transmittance of thermoplastic resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE881495A (en) * | 1979-02-05 | 1980-08-01 | Sandoz Sa | PROCESS FOR THE STABILIZATION OF POLYMERIC ORGANIC MATERIALS |
| GB2042562B (en) * | 1979-02-05 | 1983-05-11 | Sandoz Ltd | Stabilising polymers |
| EP0186628B1 (en) * | 1984-12-24 | 1989-12-13 | Ciba-Geigy Ag | Pentaerythritdiphosphites, process for their preparation and their use as stabilizers |
| JPH0759652B2 (en) * | 1985-08-07 | 1995-06-28 | 住友化学工業株式会社 | Polyolefin resin composition |
| JP2774309B2 (en) * | 1989-04-26 | 1998-07-09 | 旭電化工業株式会社 | Polyolefin resin composition |
| ES2062486T3 (en) * | 1989-08-31 | 1994-12-16 | Ciba Geigy Ag | 3-PHENYLBENZOFURAN-2-ONAS. |
-
1992
- 1992-01-27 GB GB9201705A patent/GB2252325A/en not_active Withdrawn
- 1992-01-28 DE DE4202276A patent/DE4202276A1/en not_active Withdrawn
- 1992-01-29 CA CA002060276A patent/CA2060276A1/en not_active Abandoned
- 1992-01-30 IT ITMI920177A patent/IT1255635B/en active IP Right Grant
- 1992-01-30 JP JP4040407A patent/JPH0565371A/en active Pending
- 1992-01-30 FR FR9201005A patent/FR2672292A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0565371A (en) | 1993-03-19 |
| GB2252325A (en) | 1992-08-05 |
| FR2672292A1 (en) | 1992-08-07 |
| ITMI920177A0 (en) | 1992-01-30 |
| ITMI920177A1 (en) | 1993-07-30 |
| IT1255635B (en) | 1995-11-09 |
| DE4202276A1 (en) | 1992-08-13 |
| GB9201705D0 (en) | 1992-03-11 |
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