GB2247241A - Stabilising composition for filled polymeric materials - Google Patents
Stabilising composition for filled polymeric materials Download PDFInfo
- Publication number
- GB2247241A GB2247241A GB9018427A GB9018427A GB2247241A GB 2247241 A GB2247241 A GB 2247241A GB 9018427 A GB9018427 A GB 9018427A GB 9018427 A GB9018427 A GB 9018427A GB 2247241 A GB2247241 A GB 2247241A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- groups
- component
- hydrogen
- stabilising
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 230000003019 stabilising effect Effects 0.000 title claims description 26
- 239000000463 material Substances 0.000 title claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- -1 2-cyclohexylphenyl Chemical group 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 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 4
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 229920000098 polyolefin Polymers 0.000 description 14
- 239000000945 filler Substances 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Chemical class 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- PFIQRRZEQOBIMQ-UHFFFAOYSA-N 1,2-bis(2,4-ditert-butylphenyl)biphenylene Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C=2C3=CC=CC=2)C3=C1C1=CC=C(C(C)(C)C)C=C1C(C)(C)C PFIQRRZEQOBIMQ-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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
A composition suitable as a processing stabiliser for a polymeric substrate comprises: (a) one or more phosphonites of formula I <IMAGE> (b) one or more compounds of formula II (II) S(-[OCH2)p-CO-O-R10]2 in which p is an integer of 2-6; n is 0 or 1; m is 0 or 1; Y is 0, -S-, -CH(R5), or -C6H4-; where R5 is hydrogen, C1-8alkyl or @ COOR6; where R6 is C1-8 alkyl; @each R, independently, is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups; whereby the two -OH groups are not positioned to be able to form a P-containing ring; or both groups R form a group derived from an aliphatic, alicyclic or aromatic alcohol containing two OH groups in such a position tat they can form a cyclic group with a single phosphorus atom R10 is C10-32 alkyl or C10-32 alkenyl. Component (a) may comprise a mono- and di-phosphonite of formula (I) and a phosphite of formula (RO)3-P, wherein R is as defined above. The composition may additionally comprise a phenol of formula R7OH or R8(OH)2, wherein R7 and R8 are as defined for R.
Description
IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
The invention relates to new compositions, suitable as processing stabilisers, preferably for the long term stabilisation of filled polymeric substrates.
When a polyolefin contains a filler such as talc, its stability is considerably reduced because the filler accelerates the thermal and photochemical oxidation of the polymer. It is usual to use a processing stabiliser to protect the polyolefin from thermal degradation to which it is exposed at high processing temperatures.
Usually, the polymer will also include a base stabiliser such as sterically hindered phenols,(primary antioxidants) in polyolefins.
The filler also strongly reduces the activity of such base stabilisers. Often therefore, for filled polyolefins not only a sterically hindered phenol antioxidant but also a co-stabiliser to increase its effect are used.
According to the invention there is provided a composition (hereinafter defined as a stabilising composition) suitable as a processing stabiliser for a polymeric substrate comprising:
a) one or more phosphonites of formula I (hereinafter defined as component I)
b) one or more compounds of formula II (hereinafter defined as component II) (Il) S-[(CH2)p-CO-O-R10]2
in which p is an integer of 2-6;
n is O or 1;
m is O or 1;
Y is O, -S-, -CH(R5), or -C6B4-; where R5 is hydrogen, C18alkyl or COOR6;
where R6 is C8alkyl; each R, independently, is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups; whereby the two -OH groups are not positioned to be able to form a
P-containing ring; (hereinafter defined as the monovalent significances of R); more specifically, said OH groups are attached to carbon atoms in positions such that they are unable to form an -O-P-O- moeity;
or both groups R form a group derived from an aliphatic, alicyclic or aromatic alcohol containing two OH groups in such a position that they can form a cyclic group with a single phosphorus atom (hereinafter defined as the divaient significances of R); and more specifically, said OH groups are attached to carbon atoms in positions such that they can form an -O-P-O- moeity; and Rlo is C1032alkyl or C10-32alkenyl.
Preferably R is R' where R' is an alkyl, aralkyl, aryl, alkaryl, cycloalkylaryl or aralkylaryl, preferably alkyl, aryl, aralkyl or alkaryl (hereinafter referred to as the monovalent significances of
R'); or both groups R' form a group of formula a
where phenyl groups A and B may be further substituted and Y' is -O-, -S- or -CH(R5)- where R5 is hydrogen, C1-8alkyl or COOR6 where R6 is
C1-8alkyl (hereinafter defined as the divalent significances of R') and n is O or 1.
More preferably R is Rn where R" is selected from C1-22alkyl; 2-cyclohexylphenyl; phenyl, unsubstituted or substituted by 1 to 3 groups selected from C1-22alkyl and C1-22alkixy, phenyl -C1-4alkyl (especially -C(CH3)2-C6H5 or -CH2-C6H)5; cyclohexyl 2,2,6,6-tetramethyl- piperidinyl-4-, -OH,-(C1-6alkyl)phenyl, -CO2-C122alkyl, -CH2CH2-COOR15, CN or -CH2-S-C1-22alkyl; or R" is a group of any one of formulae i to vii
or both groups R" form a group of formula viii
where R15 is hydrogen or C1-22alkyl;
Y' is as defined above
n is O or 1;
R16 is hydrogen, C1-8alkyl or -COC1-8alkyl;
R17 is hydrogen or C1-22alkyl; and
R18 is hydrogen, C122alkyl, C1-22alkoxy, -CH2-C6Hs, -C(CH3)2-C6H5, - C6H5, -OH, -CH2CH2COOR15, -(C1-6alkyl)phenyl, -CO2-C1-22alkyl, -CN,-CH2CH2-COOR15, -CH2-S-C1-22alkyl or 2,2,6,6 tetramethylpiperidinyl-4-; and
R24 is hydrogen, C1-22alkyl, OH or C1-22alkoxy,
Most preferably R is R"' where R"' is selected from a group of any one of formulae a) to g)
in which
R10 is hydrogen, C1-8alkyl, cyclohexyl C1-8alkoxy or (C1aalkyl)phenyl; R11 and R12 independently are selected from hydrogen, C12 2alkyl, alkyl)phenyl and phenyl;
or R11 may be cyclohexyl when Rlo and R12 are hydrogen;
R13 is selected from hydrogen and C1-8alkyl;
R14 is -CN or -CO2R13;; Preferred groups of formula a) are selected from 2-tert.butylphenyl; 2-phenylphenyl; 2-(1',1'-dimethyl propyl)phenyl; 2-cyclohexylphenyl; 2-tert.butyl-4-methyl phenyl; 2,4-di-tert.amyl phenyl; 2,4-di-tert.
-butyl phenyl; 2,4-diphenylphenyl; 2,4-di-tert.octyl phenyl; 2-tert.butyl-4-phenyl-phenyl; 2,4-bis(1',1'-dimethylpropyl) phenyl; 2-(1-phenyl-l-methylethyl)phenyl; 2 ,4-bis(1-phenyl-1-methylethyl) phenyl; and 2,4-ditert.butyl-6-methylphenyl.
Preferably the compound of formula I is tetrakis (2,4-di-tert.
-butyl phenyl)-biphenylene diphosphonite; (commercially available in
Sandostab PEPQ, a trademark of Sandoz Ltd.).
Preferably m is 1.
Preferably component I comprises
a) a diphosphonite of formula I defined above (hereinafter defined as component a);
b) a compound of formula VI
(R-0)3-P (VI)
where R is as defined above; (hereinafter defined as component b);
c) a monophosphonite of formula I defined above (hereinafter defined as component c).
Preferably the ratio of components a), b) and c) are
40-80X component a)
10-30% component b)
10-30% component c)
Stabilising compositions according to the invention may additionally contain d) a phenol of formula IV or V (hereinafter defined as component d) R7(OH) (IV) Rs (OH)2 2 (V) in which, in formula IV, R7 is a monovalent significance of R and Ra is a divalent significance of R (i.e. R-O- is a monovalent significance of R-O- and R-(0)2- is a divalent significance of R-O).
For the avoidance of doubt, where a symbol appears more than once in a formula or once in two different formulae of a stabilising composition according to the invention, its significances are independent unless indicated to the contrary. However, where in a stabilising composition, a symbol appears in formula I and II and optionally III, IV and V, the significances of the symbol are preferably the same.
Preferably the amount of Component I (which may include one or more of components a), b) and c) where appropriate) present in a stabilising composition according to the invention is 25 to 75X (more preferably 30-50%). Preferably the amount of Component II present in a stabilising composition according to the invention is 75-25% (more preferably 70-50X).
Further, according to the invention there is provided a polymeric composition comprising a polymeric material and a stabilising amount of a stabilising composition according to the invention.
Preferably the amount of components I and II present in such a polymeric composition are from 0.01 to 1 %; more preferably 0.05 to 0.3 X by weight based on the polymeric material.
It has been found that a combination of Components I and II in a stabilising composition according to the invention produces a synergistic effect on the stability of a polymeric composition to which it is applied. Properties such as long term stability, the melt flow index (MFI) and colour stability of such polymeric compositions are generally improved over those in which only component I or II is present (especially long term stability).
Suitable fillers include chalk, glass fibres, talc, silica, titanium and silicon dioxide or aluminium hydroxide. Preferred fillers are chalk and talc, particularly talc. Filled polyolefin is taken to be polymer containing at least 2% by wt. of filler, calculated on the total weight. Conventional filled polyolefin may however contain 10-59X wt, of filler, preferably 20-40 wt. X, calculated on the total weight.
Further polymeric materials that can be stabilised by a stabilising composition according to the invention include homopolymers,copolymers and polymer blends of:
Cellulose acetate; Cellulose acetatobutyrate; Cellulose acetopropionate; Cresol-formaldehyde resin; Carbooxmethylcellbulose; Cellulose nitrate;Cellulose propionate; Casein plastics;
Casein-formaldehyde; Cellulose triacetate; Ethyl cellulose; Epoxy resins; Methyl cellulose; Melamine-formaldehyde resins; Polyamide;
Polyamideimide; Polyacrylonitrile; Polybutene-1; Polybutylacrylate;
Poly(butyleneterephthalate); Polycarbonate; Poly(chloro trifluoroethylene); Poly(diallylphthalate); Polyethylene; chlorinated
Polyethyene; Poly(etheretherketone); Polyetherimide;
Polyethyleneoxide; Polyethersulphone; Polyethyleneterephthalate; Polytetrafluoroethylene; Phenol-formaldehyde resins;Polyimide;
Polyisobutylene; Polyisocyanurate; Polymehtacrylimide;
Polymethylmethacrylate; Poly(-4-methylpenten-1); Poly(a-methyl styrene); Polyoxymethylene; Polyformaldehyde; Polyacetal;
Polypropylene; Polyphenylene ether; Polyphenylenesulphide;
Polyphenylenesulphone; Polystyrene; Polysulphone; Polyurethane;
Polyvinylacetate; Polyvinyl alcohol; Polyvinylbutyral chlorinated
Polyvinyl chloride; Polyvinylidene chloride; Polyvinylidene fluoride;
Polyvinyl fluoride;Polyvinylformaldehyde; Polyvinylformaldehyde; Polyvinylcarbazol; Polyvinylpyrrolidone; Silicon copolymers; saturated polyester; urea-formaldehyde resins; unsaturated polyester; polyacrylate; polymethacrylate; polyacrylamide; maleinate resins; phenolic resins; aniline resins; furane resins; carbamide resins; epoxide resins and silicon resins.
Examples of suitable copolymers include:
Acrylonitrile/butadiene/acrylate; Acrylonitrile/butadiene/styrene;
Acrylonitrile/methylmethacrylate; Acrylonitrile/styrene/acrylic ester;
Acrylonitrile/ethylene-propylenediene/styrene; Acrylonitrile/chlorinated polyethylene/styrene; Ethylene/ethylacrylate; Ethylene methacrylic acid ester; Ethylene/propylene; Ethylene/propylene-diene; Ethylene/vinyl acetate; Ethylene/vinyl alcohol;Ethylene/tetrafluoroethylene;
Tetrafluoroethylene/hexafluoropropylene; Methacrylate/butadiene/styrene;
Helamine/phenol-formaldehyde; Polyester; Polyamide; Perfluoro-alkoxyalkane; Styrene/acrylonitrile; Styrene/butadiene; Styrene/maleic acid anhydride; Styrene/a-methylstyrene; Vinylchloride/ethylene;
Vinylchloride/ethylene/methacrylate; Vinylchloride/ethylene/vinyl acetate; Vinylchloride/methylmethacrylate;Vinylchloride/octylacrylate;
Vinylchloride/vinyl acetate; and Vinylchloride/vinylidene chloride.
Preferred polymeric materials to be stabilised are polyolefins such as polypropylene, polyethylene (e.g. high density polyethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polyisobutylene, poly-4-methylpentene and copolymers thereof.
Further additives that can be added to a stabilising or a polymeric composition according to the invention include antioxidants, such as sterically hindered phenols,secondary aromatic amines or organic sulfur compounds, such as described in "Kunststoff-Additive", Ga"chter/Muller, Ed. 3, 1990, p.42-50, the contents of which are incorporated herein by reference;U.V. stabilisers such as sterically hindered amines (for example N-unsubstituted, N-alkyl or N-acyl substituted 2,2,6,6tetra-methylpiperidine compounds) [also known as hindered amine light stabilisers - HALS] and U.V. absorbers (e.g. 2-(2'-hydroxyphenyl) -benztriazoles, 2-hydroxybenzophenones, 1,3-bis-(2'-hydroxybenzoyl-) benzene salicylates, cinnamates and oxalic acid diamides;), U.V.quenchers such as benzoates and substituted benzoates, antistatic agents, flameproofing agents, softeners, nucleating agents, metal deactivators, biocides, impact modifiers, pigments and fungicides.
Stabilising compositions according to the invention may be added to the polymeric material before, during or after the polymerization step and may be added in solid or molten form, in solution preferably as a liquid concentrate containing from 10 to 80 % by weight of the composition and 90 to 20 % by weight of solvent or as a solid masterbatch composition containing 10 to 80 X (more preferably 40 to 70 %) by weight of the composition and 90 to 20 % (more preferably 60 to 30 t) by weight of a solid polymeric material which is identical with or compatible with the material to be stabilized.
Polyolefin resins are generally sold by their manufactureres already base-stabilised; that is, they will normally already contain a primary stabiliser (antioxidant) based on a sterically hindered phenol. When this is the case, the filled polyolefin of the invention may be produced by mixing the compound of formula I or II and the filler with molten base-stabilised polyolefin.
This may be done in conventional manner in a single mixing operation for example in a kneader or roll mixer, or with simultaneous formation into shaped articles in an extruder or screw injection moulding machine, whereby articles such as rods, tubes, container, bottles profiles, foams and coated metal wires may be produced. Alternatively component I or II may be melt blended with one portion of polyolefin, the filler with a second portion, and the two portions are then melt-blended together.
Master batch compositions containing the polyolefin together with a high concentration of co-stabiliser and/or filler may be made and then blended into larger quantities of polyolefin. Where the polyolefin does not already contain the base stabiliser, this may be added at any stage of the melt-blending operations described above.
Other stabilisers, co-stabilisers or metal deactivators may be used in the filled polyolefin of the present invention,.but this is not necessary since the combination of the sterically hindered phenol and components I and II provide good stabilisation both during processing and in the long-term.
Further additives for examples flame retardants and antistatic agents may also be present.
The compositions according to the invention may be incorporated by known methods into the polymeric material to be stabilized. Of particular importance is blending of the compounds with thermoplastic polymers in the melt, for example in a melt blender or during the formation of shaped articles, including foils, tubes, fibres and foams by extrusion, injection moulding, blow moulding, spinning or wire coating. The compositions according to the invention are particularly useful for polypropylene articles formed by injection moulding techniques.
Further, in this specification, where a range is given, the figures defining the range are included therein. Any group capable of being linear or branched is linear or branched unless indicated to the contrary.
For the avoidance of doubt, in this specification t-butyl means tertiary butyl, (-C(CH3)3).
The invention will now be illustrated by the following Examples in which all parts and percentages are by weight and all temperatures are in degrees centigrade unless indicated to the contrary.
The invention will now be illustrated by the hollowing examples in which all temperatures are in Centigrade.
Examples 1-5
Polypropylene compositions comprising 80 parts polypropylene, 20 parts talc plus 0.1 parts per hundred resin (phr) of calcium stearate and 0.1 phr of Irganox 1010 [tetrakis (methylene-3[4'-hydroxy-3t,5t -di-tert-butyl phenyl)] propionate methane] are mixed together. To this mixture amounts of stabilising compositions described in Table 2 are added.
The polypropylene is extruded through a Göttfert extrusiometer having a 20mm screw (compression 1:3, diameter to length (d:l) = 1:20) at 2700.
Multiple extrusions are carried out under the same conditions. Melt Flow
Index (MFI) at 2300C/2.16 kp and YI (yellowness Index) are measured after each extrusion. Accelerated aging tests (oven tests) are also performed according to DIN 53383 using a tubular oven at 1500C.
The MFI and Yellowness Index are giving in Table 1 below:
Table 1
Stabilising compositions Oven Stability MFI(5-1) YI(5-1)
1 67 h ~ 2.8 days 5.08 8.6
2 422 h = 17.6 days 1.30 6.0
3 562 h = 23.4 days 2.78 5.1
4 442 h = 18.4 days 1.94 8.0
5 216 h = 9.0 days 4.68 6.6
The MFI given in Table 1 and the Yellowness Index giving in Table 1 show the difference in MFI and YI, respectively, between the fifth and the first extrusions passages (indicated by (5-1)).
Oven testing is performed at 150 on O.5mm.plaques according to DIN 53383 until surface cracking of the samples has become visible.
Excellent resistance of the polypropylene against heat and degradation is obtained.
Stabilising compositions 1 to 5 are as given in Table 2 below:
Table 2
Stabilising compositions Amount of compound in phr
1 without DSTDP or P-EPQ
2 0.15 P-EPO
3 0.05 P-EPQ + 0.10 DSTDP
4 0.10 P-EPO + 0.05 DSTDP
5 0.15 DSTDP
DSTDP is distearyl thiodipropionate and
P-EPO is a coimnercially available product from SANDOZ as Sandostab
P-EPQ of circa
a) 50-80Z tetrakis (2,4 ditertiary butyl phenyl) biphenylene
diphosphonite
b) 10-25X bis (2,4 ditertiary butylphenyl) biphenylene monophosphoni te ; - c) 10-25Z tris (2,4 -ditertiary butyl phenyl) phosphite
Examples 1, 2 and 5 do not illustrate the invention.
Claims (9)
1. A composition (hereinafter defined as a stabilising composition) suitable as a processing stabiliser for a polymeric substrate comprising:
a) one or more phosphonites of formula I (hereinafter defined as component I)
b) one or more compounds of formula II (hereinafter defined as component II)
(11)
S-[(CH2)p-CO-O-R10]2
in which p is an integer of 2-6;
n is O or 1;
m is O or 1;
Y is 0, -S-, -CH(R5), or -C6H4-;
where R5 is hydrogen, Alkyl or COOR6;
where R6 is C1~8alkyl; each R, independently, is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups; whereby the two -OH groups are not positioned to be able to form a
P-containing ring; (hereinafter defined as the monovalent significances of R);
or both groups R form a group derived from an aliphatic, alicyclic or aromatic alcohol containing two OH groups in such a position that they can form a cyclic group with a single phosphorus atom (hereinafter defined as the divalent significances of R).
Rlo is C10-32alkyl or C1032alkenyl.
2. A stabilising composition according to claim 1 in which R is
R' where R' is an alkyl, aralkyl, aryl, alkaryl, cycloalkylaryl or aralkylaryl, (hereinafter referred to as the monovalent significances of R'); or both groups R' form a group of formula a
where phenyl groups A and B may be further substituted and Y is -O-, -S- or -CH(R5)- where R5 is hydrogen, C1-8alkyl or COOR6 where R6 is C18alkyl (hereinafter defined as the divalent significances of R').
3. A stabilising compound according to claim 2 in which R is R" where R" is selected from C122alkyl; 2-cyclohexylphenyl; phenyl, unsubstituted or substituted by 1 to 3 groups selected from
C1-22alkyl, C1-22alkoxy, phenyl, C1-4alkyl (especially -C(CH3)2 -C6H5 or CH2-C6H5; cyclohexyl; 2,2,6,6-tetramethyl- piperidinyl-4-, -OH,-(C16alkyl)phenyl, -C02-C122alkyl, -CH2CH2-COOR15, CN or -CH2-S-C122alkyl; or R" is a group of any one of formulae i to vii
t.butyl R,,,Ria CY? 8 U H -CH CH3 t.butyl (ji) butyl (i) 3 H24 butyl
or both groups R" form a group of formula viii
where R15 is hydrogen or C122alkyl; Y' is -O-, -S- or -CH(R'5)-, where R5 is hydrogen, C18alkyl or COOR6 where R6 is C1-8alkyl;
n is O or 1;
R16 is hydrogen, C1-8alkyl or -COC1-8alkyl;
R17 is hydrogen or C1-22alkyl; and Ria is hydrogen, C1~22alkyl, C1~22alkoxy, -CH2-C6H5, -C(CH3)2-C6H5, - C6H5, -OH, -CH2CH2COOR15, -(C1-6alkyl)phenyl, -CO2-C1-22alkyl, -CN,-CH2CH2-COOR15, -CH2-S-C1-22alkyl or 2,2,6,6tetramethylpiperidinyl-4-; and
R24 is hydrogen, C1-22alkyl, OH or C1-22alkoxy.
4. A stabilising composition according to any one of the preceding claims in which component I comprises
a) a diphosphonite of formula I defined in Claim 1 (hereinafter defined as component a);
b) a compound of formula VI (R-O)3-P (VI)
where R is as defined in Claim 1 (hereinafter defined as component b);
c) a monophosphonite of formula I defined in Claim 1 (hereinafter defined as component c).
5. A stabilising composition according to claim 4 in which the ratio of components a), b) and c) are: 40-80X component a) 10-30X component b)
10-30X component c)
6. A stabilising composition according to any one of the preceding claims additionally containing a phenol of formula IV or V (defined as compound d) R,(OH) (IV)
R8(OH)2 (V)
in which, in formula IV, R7 is a monovalent significance of R and Ra is a divalent significance of R; R being as defined in Claim 1.
7. A stabilising composition substantially as herein described with reference to Example 2 or 3.
8. A polymeric composition comprising a polymeric material and a stabilising amount of a stabilising composition according to any of the preceding claims
9. A polymeric composition according to claim 8 in which the amounts of components I and II is from 0.01 to 1% based on the weight of polymeric material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9018427A GB2247241A (en) | 1990-08-22 | 1990-08-22 | Stabilising composition for filled polymeric materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9018427A GB2247241A (en) | 1990-08-22 | 1990-08-22 | Stabilising composition for filled polymeric materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9018427D0 GB9018427D0 (en) | 1990-10-03 |
| GB2247241A true GB2247241A (en) | 1992-02-26 |
Family
ID=10681055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9018427A Withdrawn GB2247241A (en) | 1990-08-22 | 1990-08-22 | Stabilising composition for filled polymeric materials |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2247241A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405891A (en) * | 1992-12-04 | 1995-04-11 | Ciba-Geigy Corporation | Oligomeric HALS phosphites and HALS phosphonites as stabilisers |
| US5442067A (en) * | 1992-09-25 | 1995-08-15 | Ciba-Geigy Corporation | Tetra-[N-alkyl-2,2,6,6,-tetramethylpiperidin-4-yl]-4,4'-diphenylbisphosphonite |
| GB2288397A (en) * | 1994-04-13 | 1995-10-18 | Ciba Geigy Ag | HALS phosphonites as stabilizers |
| GB2263280B (en) * | 1992-01-17 | 1996-07-31 | Sandoz Ltd | Use of a phosphonite and optionally a phosphite for clarifying propylene polymers |
| GB2265377B (en) * | 1992-03-11 | 1996-07-31 | Sandoz Ltd | The use of phosphonite-HALS and phosphite-HALS compounds for the stabilisation of polyolefins |
| US5616636A (en) * | 1992-03-11 | 1997-04-01 | Sandoz Ltd. | Phosphonite-hals and phosphite-hals compounds as stabilizers |
| US5654430A (en) * | 1994-04-13 | 1997-08-05 | Ciba-Geigy Corporation | Oligomeric aliphatic HALS phosphites and HALS phosphonites as stabilizers |
| US5777113A (en) * | 1994-10-12 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Hals phosphorinanes as stabilisers |
| US5777008A (en) * | 1994-06-02 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Oligomeric hals phosphites and hals phosphonites as stabilisers |
| EP0926203A1 (en) * | 1997-12-23 | 1999-06-30 | General Electric Company | Stabilized polyetherimide resin composition |
| US5925758A (en) * | 1994-04-13 | 1999-07-20 | Ciba Specialty Chemicals Corporation | HALS phosphites and HALS phosphoramides as stabilizers |
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| US3824192A (en) * | 1969-08-29 | 1974-07-16 | A Dibattista | Stabilized system containing metal hydroxyalkyl phosphonic acid or phosphinic acid |
| US3951912A (en) * | 1974-04-05 | 1976-04-20 | American Cyanamid Company | Hydroxybenzylphosphonate antioxidants |
| US4077940A (en) * | 1976-09-14 | 1978-03-07 | Chevron Research Company | Thermal stabilization of polypyrrolidone against reversion to monomer |
| EP0054308A1 (en) * | 1980-12-17 | 1982-06-23 | Amoco Corporation | Stabilized polyarylate compositions |
| EP0151327A1 (en) * | 1984-01-06 | 1985-08-14 | SOLVAY & Cie (Société Anonyme) | Stabilized compositions based on alpha-olefin polymers |
| EP0158501A2 (en) * | 1984-04-02 | 1985-10-16 | Polyplastics Co. Ltd. | Method of preparation of polyester |
| JPS6136870B2 (en) * | 1982-06-22 | 1986-08-20 | Sanko Kagaku Kk | |
| GB2184733A (en) * | 1985-12-18 | 1987-07-01 | Basf Corp | Stabilizer package for the preparation of thermoplastic polyurethane having improved high temperature color stability |
| JPS6234254B2 (en) * | 1981-03-31 | 1987-07-25 | Showa Denko Kk | |
| EP0238140A2 (en) * | 1986-03-19 | 1987-09-23 | Akzo N.V. | Polyester resin composition with excellent heat resistance |
| US4801757A (en) * | 1987-11-27 | 1989-01-31 | Ici Americas Inc. | Noncrystalline tris(4-hydroxy-2-methyl-5-tert. butylphenyl) butane |
| GB2215727A (en) * | 1988-02-15 | 1989-09-27 | Sandoz Ltd | Stabilisers for polymers |
| GB2227490A (en) * | 1989-01-24 | 1990-08-01 | Sandoz Ltd | Polymer stabilisers |
-
1990
- 1990-08-22 GB GB9018427A patent/GB2247241A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3824192A (en) * | 1969-08-29 | 1974-07-16 | A Dibattista | Stabilized system containing metal hydroxyalkyl phosphonic acid or phosphinic acid |
| US3951912A (en) * | 1974-04-05 | 1976-04-20 | American Cyanamid Company | Hydroxybenzylphosphonate antioxidants |
| US4077940A (en) * | 1976-09-14 | 1978-03-07 | Chevron Research Company | Thermal stabilization of polypyrrolidone against reversion to monomer |
| EP0054308A1 (en) * | 1980-12-17 | 1982-06-23 | Amoco Corporation | Stabilized polyarylate compositions |
| JPS6234254B2 (en) * | 1981-03-31 | 1987-07-25 | Showa Denko Kk | |
| JPS6136870B2 (en) * | 1982-06-22 | 1986-08-20 | Sanko Kagaku Kk | |
| EP0151327A1 (en) * | 1984-01-06 | 1985-08-14 | SOLVAY & Cie (Société Anonyme) | Stabilized compositions based on alpha-olefin polymers |
| US4829110A (en) * | 1984-01-06 | 1989-05-09 | Solvay & Cie (Societe Anonyme) | Stabilized compositions based on alpha-olefin polymers |
| EP0158501A2 (en) * | 1984-04-02 | 1985-10-16 | Polyplastics Co. Ltd. | Method of preparation of polyester |
| GB2184733A (en) * | 1985-12-18 | 1987-07-01 | Basf Corp | Stabilizer package for the preparation of thermoplastic polyurethane having improved high temperature color stability |
| EP0238140A2 (en) * | 1986-03-19 | 1987-09-23 | Akzo N.V. | Polyester resin composition with excellent heat resistance |
| US4801757A (en) * | 1987-11-27 | 1989-01-31 | Ici Americas Inc. | Noncrystalline tris(4-hydroxy-2-methyl-5-tert. butylphenyl) butane |
| GB2215727A (en) * | 1988-02-15 | 1989-09-27 | Sandoz Ltd | Stabilisers for polymers |
| GB2227490A (en) * | 1989-01-24 | 1990-08-01 | Sandoz Ltd | Polymer stabilisers |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2263280B (en) * | 1992-01-17 | 1996-07-31 | Sandoz Ltd | Use of a phosphonite and optionally a phosphite for clarifying propylene polymers |
| 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 |
| US5442067A (en) * | 1992-09-25 | 1995-08-15 | Ciba-Geigy Corporation | Tetra-[N-alkyl-2,2,6,6,-tetramethylpiperidin-4-yl]-4,4'-diphenylbisphosphonite |
| US5405891A (en) * | 1992-12-04 | 1995-04-11 | Ciba-Geigy Corporation | Oligomeric HALS phosphites and HALS phosphonites as stabilisers |
| US5654430A (en) * | 1994-04-13 | 1997-08-05 | Ciba-Geigy Corporation | Oligomeric aliphatic HALS phosphites and HALS phosphonites as stabilizers |
| GB2288397A (en) * | 1994-04-13 | 1995-10-18 | Ciba Geigy Ag | HALS phosphonites as stabilizers |
| US5665273A (en) * | 1994-04-13 | 1997-09-09 | Ciba-Geigy Corporation | Hals phosphonites as stabilizers |
| GB2288397B (en) * | 1994-04-13 | 1997-12-17 | Ciba Geigy Ag | HALs phosphonites as stabilizers |
| RU2132852C1 (en) * | 1994-04-13 | 1999-07-10 | Циба Спешиалти Кемикалс Холдинг, Инк. | Aliphatic oligomeric phosphites or phosphonites, method of preparation thereof, polymeric composition containing thereof, and method of stabilization |
| US5925758A (en) * | 1994-04-13 | 1999-07-20 | Ciba Specialty Chemicals Corporation | HALS phosphites and HALS phosphoramides as stabilizers |
| US5777008A (en) * | 1994-06-02 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Oligomeric hals phosphites and hals phosphonites as stabilisers |
| US5777113A (en) * | 1994-10-12 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Hals phosphorinanes as stabilisers |
| EP0926203A1 (en) * | 1997-12-23 | 1999-06-30 | General Electric Company | Stabilized polyetherimide resin composition |
| SG166663A1 (en) * | 1997-12-23 | 2010-12-29 | Gen Electric | Stabilized polyetherimide resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9018427D0 (en) | 1990-10-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |