US20030197151A1 - Stabilizer mixtures - Google Patents
Stabilizer mixtures Download PDFInfo
- Publication number
- US20030197151A1 US20030197151A1 US10/276,120 US27612002A US2003197151A1 US 20030197151 A1 US20030197151 A1 US 20030197151A1 US 27612002 A US27612002 A US 27612002A US 2003197151 A1 US2003197151 A1 US 2003197151A1
- Authority
- US
- United States
- Prior art keywords
- rtm
- formula
- compound
- tinuvin
- hydrogen
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000003381 stabilizer Substances 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 361
- 239000001257 hydrogen Substances 0.000 claims abstract description 234
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 234
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 211
- -1 amine compounds Chemical class 0.000 claims abstract description 88
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 37
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 52
- 150000002431 hydrogen Chemical class 0.000 claims description 22
- 239000011368 organic material Substances 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000003031 C5-C7 cycloalkylene group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- 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
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000005447 octyloxy 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])O* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- GUCMKIKYKIHUTM-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]piperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN1C(=O)C(C)(C)NC(C)(C)C1 GUCMKIKYKIHUTM-UHFFFAOYSA-N 0.000 description 561
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 343
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 70
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 47
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 47
- CMXLJKWFEJEFJE-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound C1=CC(OC)=CC=C1C=C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(=O)OC1CC(C)(C)N(C)C(C)(C)C1 CMXLJKWFEJEFJE-UHFFFAOYSA-N 0.000 description 42
- OLBWDGJTEXRJLY-UHFFFAOYSA-N tetradecyl 3-(2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazadispiro[5.1.11^{8}.2^{6}]henicosan-20-yl)propanoate Chemical compound O1C2(CCCCCCCCCCC2)N(CCC(=O)OCCCCCCCCCCCCCC)C(=O)C21CC(C)(C)NC(C)(C)C2 OLBWDGJTEXRJLY-UHFFFAOYSA-N 0.000 description 36
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 34
- 229920001577 copolymer Polymers 0.000 description 34
- 239000004611 light stabiliser Substances 0.000 description 30
- 150000003254 radicals Chemical class 0.000 description 30
- GMBXBKNMMIWUED-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-4-yl)-3-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]propanamide Chemical compound C1C(C)(C)NC(C)(C)CC1NCCC(=O)NC1CC(C)(C)NC(C)(C)C1 GMBXBKNMMIWUED-UHFFFAOYSA-N 0.000 description 27
- IVVLFHBYPHTMJU-UHFFFAOYSA-N 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11^{8}.2^{6}]henicosan-21-one Chemical compound C1C(C)(C)NC(C)(C)CC21C(=O)NC1(CCCCCCCCCCC1)O2 IVVLFHBYPHTMJU-UHFFFAOYSA-N 0.000 description 26
- 239000013065 commercial product Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 0 *C(CN1C(C)(C)CC(OC)CC1(C)C)OOCCC(C)=O Chemical compound *C(CN1C(C)(C)CC(OC)CC1(C)C)OOCCC(C)=O 0.000 description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 9
- FJZKADZLSJRAQF-UHFFFAOYSA-N CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 Chemical compound CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 FJZKADZLSJRAQF-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- RNTWWGNZUXGTAX-UHFFFAOYSA-N CCC(C)C(C)CC Chemical compound CCC(C)C(C)CC RNTWWGNZUXGTAX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- IGJZIHFHGBCTLK-UHFFFAOYSA-N CCC(O)CNC1CC(C)(C)N(C)C(C)(C)C1 Chemical compound CCC(O)CNC1CC(C)(C)N(C)C(C)(C)C1 IGJZIHFHGBCTLK-UHFFFAOYSA-N 0.000 description 5
- AHWDQDMGFXRVFB-UHFFFAOYSA-N CN1C(=O)N(C)C(=O)N(C)C1=O Chemical compound CN1C(=O)N(C)C(=O)N(C)C1=O AHWDQDMGFXRVFB-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 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 4
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- YEWBOZCFGXOUQW-UHFFFAOYSA-N 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-ylmethanol Chemical compound C1OP2OCC1(CO)CO2 YEWBOZCFGXOUQW-UHFFFAOYSA-N 0.000 description 4
- KXPXKNBDCUOENF-UHFFFAOYSA-N 2-(Octylthio)ethanol Chemical compound CCCCCCCCSCCO KXPXKNBDCUOENF-UHFFFAOYSA-N 0.000 description 4
- ZPIRWAHWDCHWLM-UHFFFAOYSA-N 2-dodecylsulfanylethanol Chemical compound CCCCCCCCCCCCSCCO ZPIRWAHWDCHWLM-UHFFFAOYSA-N 0.000 description 4
- CKPKHTKLLYPGFM-UHFFFAOYSA-N 6,6-dimethylheptane-1,1-diol Chemical compound CC(CCCCC(O)O)(C)C CKPKHTKLLYPGFM-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VNGRFKHOGGDZRI-UHFFFAOYSA-N CCC(O)CN1C(C)(C)CC2(CC1(C)C)OC1(CCCCCCCCCCC1)N(C)C2=O.[H]N1C(C)(C)CC2(CC1(C)C)OC1(CCCCCCCCCCC1)N(CC(C)COC)C2=O Chemical compound CCC(O)CN1C(C)(C)CC2(CC1(C)C)OC1(CCCCCCCCCCC1)N(C)C2=O.[H]N1C(C)(C)CC2(CC1(C)C)OC1(CCCCCCCCCCC1)N(CC(C)COC)C2=O VNGRFKHOGGDZRI-UHFFFAOYSA-N 0.000 description 4
- ADKOZMAWHPEEOZ-UHFFFAOYSA-N CN1C(C)(C)CC(N2CN3C(=O)N4CN(C5CC(C)(C)N(C)C(C)(C)C5)CN5C(=O)N(C2)C3C45)CC1(C)C Chemical compound CN1C(C)(C)CC(N2CN3C(=O)N4CN(C5CC(C)(C)N(C)C(C)(C)C5)CN5C(=O)N(C2)C3C45)CC1(C)C ADKOZMAWHPEEOZ-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 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 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- FPQJEXTVQZHURJ-UHFFFAOYSA-N n,n'-bis(2-hydroxyethyl)oxamide Chemical compound OCCNC(=O)C(=O)NCCO FPQJEXTVQZHURJ-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WNOWBRDWVSDLDV-UHFFFAOYSA-N CC(C)(CN1C)N(C)C(C)(C)C1=O Chemical compound CC(C)(CN1C)N(C)C(C)(C)C1=O WNOWBRDWVSDLDV-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920002396 Polyurea Polymers 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003839 salts Chemical class 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical compound CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- ZQMPWXFHAUDENN-UHFFFAOYSA-N 1,2-bis[(2-methylphenyl)amino]ethane Natural products CC1=CC=CC=C1NCCNC1=CC=CC=C1C ZQMPWXFHAUDENN-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
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- VPYDVGWWXAYRPP-UHFFFAOYSA-N 1-[2-[[4,6-bis[cyclohexyl-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]amino]-1,3,5-triazin-2-yl]-cyclohexylamino]ethyl]-3,3,5,5-tetramethylpiperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN(C=1N=C(N=C(N=1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)C1CCCCC1 VPYDVGWWXAYRPP-UHFFFAOYSA-N 0.000 description 2
- 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 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
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- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/26—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
Definitions
- the present invention relates to a stabilizer mixture containing a specific sterically hindered amine ester or amide, and two different low molecular weight sterically hindered amines.
- Stabilizer mixtures containing blends of sterically hindered amines are for example described in U.S. Pat. No. 4,692,468, U.S. Pat. No. 4,863,981, U.S. Pat. No. 5,719,217, U.S. Pat. No. 5,919,399, U.S. Pat. No. 5,965,643, U.S. Pat. No. 5,980,783, U.S. Pat. No. 6,015,849 and U.S. Pat. No. 6,020,406.
- the present invention relates to a stabilizer mixture containing the components (A) and (B)
- component (A) is
- a 1 is hydrogen or C 1 -C 4 alkyl
- a 2 is a direct bond or C 1 -C 10 alkylene
- n 1 is a number from 2 to 50;
- n 2 and n 2 * are a number from 2 to 50;
- a 3 and A 4 independently of one another are hydrogen or C 1 -C 8 alkyl, or A 3 and A 4 together form a C 2 -C 14 alkylene group, and
- n 3 independently of one another are a number from 1 to 50;
- n 4 is a number from 2 to 50
- a 5 is hydrogen or C 1 -C 4 alkyl
- radicals A 6 and A 7 independently of one another are C 1 -C 4 alkyl or a group of the formula (a-I)
- a 8 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
- radicals A 7 are a group of the formula (a-I); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
- the compounds of component (B) have a molecular weight up to 1,000 g/mol, for example 155 to 800 g/mol or 155 to 1,000 g/mol or 300 to 800 g/mol or 300 to 1,000 g/mol.
- the two different compounds of component (B) are preferably selected from the group consisting of the following classes
- E 1 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
- m 1 is 1, 2 or 4,
- E 2 is C 1 -C 14 alkylene or a group of the formula (b-I)
- E 3 is C 1 -C 10 alkyl or C 2 -C 10 alkenyl
- E 4 is C 1 -C 10 alkylene
- E 5 and E 6 independently of one another are C 1 -C 4 alkyl, cyclohexyl or methylcyclohexyl
- E 2 is C 4 -C 10 alkanetetrayl
- two of the radicals E 7 are —COO—(C 1 -C 20 alkyl), and
- E 9 and E 10 together form C 2 -C 14 alkylene
- E 11 is hydrogen or a group -Z 1 -COO-Z 2 ,
- Z 1 is C 2 -C 14 alkylene
- Z 2 is C 1 -C 24 alkyl
- E 12 has one of the meanings of E 1 ;
- radicals E 14 independently of one another are hydrogen or C 1 -C 12 alkyl
- E 15 is C 1 -C 10 alkylene or C 3 -C 10 alkylidene
- radicals E 16 independently of one another have one of the meanings of E 1 ;
- E 17 is C 1 -C 24 alkyl
- E 18 has one of the meanings of E 1 ;
- E 19 , E 20 and E 21 independently of one another are a group of the formula (b-III)
- E 22 has one of the meanings of E 1 ;
- E 24 is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkoxy
- m 2 is 1, 2 or 3
- E 25 has one of the meanings of E 1 , and
- E 26 is C 2 -C 22 alkylene
- E 26 is a group of the formula (b-IV)
- radicals E 27 independently of one another are C 2 -C 12 alkylene, and the radicals E 28 independently of one another are C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl;
- the radicals E 29 independently of one another have one of the meanings of E 1 , and E 30 is C 2 -C 22 alkylene, C 5 -C 7 cycloalkylene, C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), phenylene or phenylenedi(C 1 -C 4 alkylene); or
- E 31 is C 1 -C 10 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl or C 1 -C 10 alkyl-substituted phenyl,
- E 32 is C 3 -C 10 alkylene
- E 33 has one of the meanings of E 1 , and
- m 3 is a number from 2 to 6.
- One of the preferred embodiments of this invention relates to stabilizer mixtures wherein the two compounds of component (B) are selected from different classes.
- component (B) are:
- alkyl having up to 25 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl
- a 8 , E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 and E 33 is C 1 -C 4 alkyl, especially methyl.
- alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
- One of the preferred meanings of E 1 is octoxy.
- E 24 is preferably C 1 -C 4 alkoxy.
- C 5 -C 12 cycloalkyl examples are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.
- C 1 -C 4 Alkyl-substituted C 5 -C 12 cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
- C 5 -C 12 cycloalkoxy examples are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
- C 1 -C 10 Alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl.
- C 7 -C 9 phenylalkyl are benzyl and phenylethyl.
- C 7 -C 9 Phenylalkyl which is substituted on the phenyl radical by 1, 2 or 3 C 1 -C 4 alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
- alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred.
- the carbon atom in position 1 is preferably saturated.
- acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl.
- C 1 -C 8 Alkanoyl, C 3 -C 8 alkenyl and benzoyl are preferred.
- Acetyl and acryloyl are especially preferred.
- alkylene having up to 22 carbon atoms examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
- C 3 -C 10 alkylidene is the group
- C 4 -C 10 alkanetetrayl is 1,2,3,4-butanetetrayl.
- C 5 -C 7 cycloalkylene is cyclohexylene.
- C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene) is methylenedicyclohexylene.
- phenylenedi(C 1 -C 4 alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
- n 1 , n 2 , n 2 * and n 4 are preferably a number from 2 to 25, in particular 2 to 20.
- n 3 is preferably a number from 1 to 25, in particular 1 to 20.
- m 3 is preferably a number from 2 to 6 or 2 to 5, in particular 2 to 4.
- Component (A) is preferably TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) or FERRO AM 806 (RTM).
- the compounds of component (B) are preferably selected from the group consisting of DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31(RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 ⁇ 128 (RTM), UVINUL 4050 H (RTM), UVASIL 299 LM (RTM) and UVASIL 2000 LM
- terminal groups which saturate the free valences in the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-4) and (B-11) depend on the processes used for their preparation.
- the terminal groups can also be modified after the preparation of the compounds.
- a 1 is hydrogen or methyl
- a dicarboxylic acid diester of the formula Y—OOC-A 2 -COO—Y in which Y is, for example, methyl, ethyl or propyl, and A 2 is as defined above
- the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or —CO-A 2 -COO—Y
- the terminal group bonded to the diacyl radical is —O—Y or
- the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a
- the terminal group bonded to the dimethylene radical can be, for example, —OH
- the terminal group bonded to the oxygen can be, for example, hydrogen.
- the terminal groups can also be polyether radicals.
- the end group bonded to the —CH 2 — residue can be, for example, hydrogen and the end group bonded to the —CH(CO 2 A 7 ) residue can be, for example, —CH ⁇ CH—COOA 7 .
- the terminal group bonded to the silicon atom can be, for example, (E 31 ) 3 Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(E 31 ) 3 .
- the compounds of the formula (B-11) can also be in the form of cyclic compounds if m 3 is a number from 3 to 6, i.e. the free valences shown in the structural formula then form a direct bond.
- a 8 is preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
- E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 and E 33 are preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
- a 8 , E 1 , E 8 , E 12 , E 13 , E16, E 18 , E 22 , E 23 , E 25 , E 29 and E 33 are in particular hydrogen or methyl and E 1 additionally is C 1 -C 8 alkoxy.
- a 1 is hydrogen or methyl
- a 2 is a direct bond or C 2 -C 6 alkylene
- n 1 is a number from 2 to 25;
- n 2 and n 2 * are a number from 2 to 25;
- a 3 and A 4 independently of one another are hydrogen or C 1 -C 4 alkyl, or A 3 and A 4 together form a C 9 -C 13 alkylene group, and
- n 3 independently of one another are a number from 1 to 25;
- n 4 is a number from 2 to 25,
- a 5 and A 6 independently of one another are C 1 -C 4 alkyl
- a 7 is C 1 -C 4 alkyl or a group of the formula (a-I)
- m 1 is 1, 2 or 4,
- E 2 is C 2 -C 10 alkylene or a group of the formula (b-I)
- E 3 is C 1 -C 4 alkyl
- E 4 is C 1 -C 6 alkylene
- E 5 and E 6 independently of one another are C 1 -C 4 alkyl
- E 2 is C 4 -C 8 alkanetetrayl
- two of the radicals E 7 are —COO—(C 10 -C 15 alkyl), and
- two of the radicals E 7 are a group of the formula (b-II);
- E 9 and E 10 together form C 9 -C 13 alkylene
- E 11 is hydrogen or a group -Z 1 -COO-Z 2 ,
- Z 1 is C 2 -C 6 alkylene
- Z 2 is C 10 -C 16 alkyl
- E 14 is hydrogen
- E 15 is C 2 -C 6 alkylene or C 3 -C 5 alkylidene
- E 17 is C 10 -C 14 alkyl
- E 24 is C 1 -C 4 alkoxy
- m 2 is 1, 2 or 3
- E 26 is a group of the formula (b-IV)
- radicals E 27 independently of one another are C 2 -C 6 alkylene, and
- radicals E 28 independently of one another are C 1 -C 4 alkyl or C 5 -C 8 cycloalkyl;
- E 30 is C 2 -C 8 alkylene
- E 31 is C 1 -C 4 alkyl
- E 32 is C 3 -C 6 alkylene
- m 3 is a number from 2 to 6.
- a particularly preferred embodiment of this invention relates to a stabilizer mixture wherein
- component (A) is a compound of the formula (A-1-a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
- n 1 is a number from 2 to 20;
- n 2 and n 2 * are a number from 2 to 20;
- n 3 independently of one another are a number from 1 to 20;
- n 4 is a number from 2 to 20
- radicals A 7 are a group of the formula (a-I)
- a 8 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
- component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11-a);
- E 1 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl;
- E 8 has one of the meanings of E 1 ;
- E 12 has one of the meanings of E 1 ;
- E 13 has one of the meanings of E 1 ;
- E 16 has one of the meanings of E 1 ;
- E 18 has one of the meanings of E 1 ;
- E 22 has one of the meanings of E 1 ;
- E 23 has one of the meanings of E 1 ;
- E 25 has one of the meanings of E 1 ;
- E 29 has one of the meanings of E 1 ;
- a particularly preferred embodiment of this invention also relates to a stabilizer mixture wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen.
- Another preferred embodiment of this invention relates to a stabilizer mixture wherein
- component (A) is a compound of the formula (A-1-a) with n 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n 2 and n 2 * are a number from 2 to 20; and
- one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen.
- a further particularly preferred embodiment of this invention is a stabilizer mixture wherein
- component (A) is a compound of the formula (A-1-a) with n 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n 2 and n 2 * are a number from 2 to 20;
- one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen;
- the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E 1 being hydrogen, (B-1-b) with E 1 being methyl, (B-1-d) with E 1 being hydrogen or methyl, (B-3-a) with E 12 being hydrogen, (B-3-b) with E 12 being hydrogen, (B-4-b) with E 13 being hydrogen, (B-5) with E 16 being hydrogen, (B-6-a) with E 18 being hydrogen or methyl, (B-8-a) with E 23 being methyl, (B-9-c) with E 25 being hydrogen or methyl, (B-10-a) with E 29 being hydrogen, or (B-11-a) with E 33 being hydrogen.
- Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products:
- stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b)
- n 2 and n 2 * are a number from 2 to 20.
- stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-4-a)
- n 4 is a number from 2 to 20, and at least 50% of the radicals A 7 are a group of the formula
- Combinations of particular interest are numbers 1, 4, 7, 8, 12, 13 and 15 to 24, and the corresponding combinations wherein TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b).
- TINUVIN 770 corresponds to the compound of the formula (B-1-b) wherein E 1 is hydrogen.
- TINUVIN 765 corresponds to the compound of the formula (B-1-b) wherein E 1 is methyl.
- TINUVIN 123 corresponds to the compound of the formula (B-1-b) wherein E 1 is octyloxy.
- TINUVIN 144 corresponds to the compound of the formula (B-1-c) wherein E 1 is methyl.
- HOSTAVIN N 24 corresponds to the compound of the formula (B-3-b) wherein E 12 is hydrogen.
- RTM The commercial product SANDUVOR 3050 (RTM) corresponds to the compound of the formula (B-3-b-1) shown below, wherein E 12 is hydrogen.
- the commercial product SUMISORB TM 61 corresponds to the compound of the formula (B-4-b) wherein E 13 is hydrogen.
- UVASIL 299 LM (RTM) or UVASIL 2000 LM (RTM) contains as active ingredient the compound of the formula (B-11-a) wherein R 16 is hydrogen.
- the compound of the formula (B-3-b-1) has the following structure:
- the stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation.
- organic materials are the following:
- Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
- HDPE high density polyethylene
- HDPE-HMW high density and high molecular weight polyethylene
- HDPE-UHMW high density and ultrahigh molecular weight polyethylene
- MDPE medium density polyethylene
- LDPE low density polyethylene
- LLDPE linear low density poly
- Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
- These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
- These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
- These catalysts may be soluble or insoluble in the polymerisation medium.
- the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table.
- the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
- These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
- Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts
- Hydrocarbon resins for example C 5 -C 9
- hydrogenated modifications thereof e.g. tackifiers
- mixtures of polyalkylenes and starch
- Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styren
- Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
- halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlor
- Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrilel butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
- Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
- Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 619, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetram
- Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
- Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
- Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
- Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
- Blends of the aforementioned polymers for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
- polyblends for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS
- Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
- synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
- Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
- This invention therefore additionally relates to a composition
- a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described herein above.
- a further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described herein above.
- the organic material is preferably a synthetic polymer, in particular from one of the above groups.
- Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer and a polypropylene copolymer are particularly preferred.
- the compounds of components (A) and (B) may be added to the organic material to be stabilized either individually or mixed with one another.
- Each of the compounds of components (A) and (B) may be present in the organic material in an amount of preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material.
- the weight ratio of the components (A):(B) is preferably 10:1 to 1:100, in particular 10:1 to 1:10 or 5:1 to 1:5. Further examples for the weight ratio are also 1:1 to 1:10, for example 1:2 to 1:5.
- the weight ratio of the two components forming component (B) is for example 1:10 to 10:1 or 1:5 to 5:1, preferably 1:2 to 2:1, in particular 1:1.
- the above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent.
- the components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
- the compounds of components (A) and (B) can be blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.
- the materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.
- the stabilized material may additionally also contain various conventional additives, for example:
- Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl
- Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
- Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
- 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-
- Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
- Hydroxylated thiodiphenyl ethers for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
- 2,2′-thiobis(6-tert-butyl-4-methylphenol 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-
- Alkylidenebisphenols for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -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-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)
- O—, N— and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
- S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-
- 1.8. Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
- Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5
- Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
- Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6
- Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
- esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-triox
- esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-triox
- esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
- esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
- Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-N-phenyl
- R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotraizol-2-ylphenyl, 2-[2′-hydroxy-3′-( ⁇ , ⁇ -dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-( ⁇ , ⁇ -dimethylbenzyl)phenyl]benzotriazole.
- esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
- 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 the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
- additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate,
- Oxamides for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
- Metal deactivators for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
- N,N′-diphenyloxamide N
- Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, dilsodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaeryth
- Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
- Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
- Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
- Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
- esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
- mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyldithiocarbamate
- dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecylmercap
- Polyamide stabilisers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
- Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
- Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
- Nucleatina agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
- inorganic substances such as talcum
- metal oxides such as titanium dioxide or magnesium oxide
- phosphates carbonates or sulfates of, preferably, alkaline earth metals
- organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
- polymeric compounds such as ionic copoly
- Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
- additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
- the weight ratio of the total amount of components (A) and (B) to the total amount of the conventional additives can be, for example, 100:1 to 1:100 or 10:1 to 1:10.
- TINUVIN 770 (RTM):
- the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm ⁇ 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying).
- T 0.1 The exposure time (T 0.1 ) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system.
- the values obtained are summarized in Table 1. High T 0.1 values are desired.
- TABLE 1 T 0.1 in hours
- the amount amount of the of the light light stabilizers stabilizers used is used is 0.075% 0.05% Light stabilizer system each*). each*).
- TINUVIN 770 RTM + TINUVIN 765 (RTM) 1780 3095 TINUVIN 770 (RTM) + TINUVIN 144 (RTM) 1990 2815 TINUVIN 770 (RTM) + TINUVIN 123 (RTM) 1780 2650 TINUVIN 770 (RTM) + HOSTAVIN N 20 2760 3205 (RTM) TINUVIN 770 (RTM) + ADK STAB LA 57 2245 3045 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3034 2440 3570 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3150 2715 3230 (RTM) TINUVIN 770 (RTM) + Compound (B-6-a-1) 1930 3095 TINUVIN 770 (RTM) + Compound (B-6-a-2) 2000 3400 TINUVIN 770 (RTM) + Compound (B-10-a-1) 3510 3940 TINUVIN 770 (RTM) +
- the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm ⁇ 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying).
- T 0.1 The exposure time (T 0.1 ) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system.
- the values obtained are summarized in the following tables. High T 0.1 values are desired.
- TABLE 2A T 0.1 T 0.1 T 0.1 in hours in hours in hours
- RTM Light Light Light stabilizer stabilizer stabilizer system in system in system in combi- combi- combi- nation nation with with with with TINUVIN TINUVIN TINUVIN 622 622 622 622 (RTM) (RTM)
- RTM The amount amount amount of the of the of the stabilizers stabilizers stabilizers of the of the of the light light light T 0.1 stabilizer stabilizer stabilizer in hours system system system system The is 0.05% is 0.07
- TINUVIN 770 RTM + 4635 6025 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4935 6080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5105 6005 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 5450 6800 ADK STAB LA 57 (RTM) TINUVIN 770 (RTM) + 6925 7735 GOODRITE UV 3034 (RTM) TINUVIN 770 (RTM) + 6530 7335 Compound (B-6-a-2) TINUVIN 770 (RTM) + 6040 6905 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5070 >6495 SANDUVOR 3050 (RTM)
- TINUVIN 770 (RTM) + 4815 >7260 TINUVIN 765 (RTM) TINUVIN 770 (RTM) + 5695 7145 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4670 7080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5390 6710 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 6655 >7260 ADK STAB LA 52 (RTM) TINUVIN 770 (RTM) + 5040 6760 ADK STAB LA 62 (RTM) TINUVIN 770 (RTM) + 5010 6205 ADK STAB LA 67 (RTM) TINUVIN 770 (RTM) + 5825 >7260 Compound (B-10-a-1) TINUVIN 770 (RTM) + 6125 7215 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5690 >7260 SANDUV
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Abstract
A stabilizer mixture containing the components (A) and (B) wherein component (A) is for example a compound of the formula (A-1) wherein A1 is hydrogen or C1-C4alkyl, A2 is a direct bond or C1-C10alkylene, and n1 is a number from 2 to 50; and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) and (II); with the proviso that components (A) and (B) are different.
Description
- The present invention relates to a stabilizer mixture containing a specific sterically hindered amine ester or amide, and two different low molecular weight sterically hindered amines.
- Stabilizer mixtures containing blends of sterically hindered amines are for example described in U.S. Pat. No. 4,692,468, U.S. Pat. No. 4,863,981, U.S. Pat. No. 5,719,217, U.S. Pat. No. 5,919,399, U.S. Pat. No. 5,965,643, U.S. Pat. No. 5,980,783, U.S. Pat. No. 6,015,849 and U.S. Pat. No. 6,020,406.
- The present invention relates to a stabilizer mixture containing the components (A) and (B)
- wherein
- component (A) is
-
- wherein
- A1 is hydrogen or C1-C4alkyl,
- A2 is a direct bond or C1-C10alkylene, and
- n1 is a number from 2 to 50;
-
- wherein
- n2 and n2* are a number from 2 to 50;
-
- wherein
- A3 and A4 independently of one another are hydrogen or C1-C8alkyl, or A3 and A4 together form a C2-C14alkylene group, and
- the variables n3 independently of one another are a number from 1 to 50; or
-
- wherein
- n4 is a number from 2 to 50,
- A5 is hydrogen or C1-C4alkyl,
-
- wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
-
- with the proviso that components (A) and (B) are different.
- Preferably the compounds of component (B) have a molecular weight up to 1,000 g/mol, for example 155 to 800 g/mol or 155 to 1,000 g/mol or 300 to 800 g/mol or 300 to 1,000 g/mol.
- The two different compounds of component (B) are preferably selected from the group consisting of the following classes
-
- in which
- E1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
- m1 is 1, 2 or 4,
- if m1 is 1, E2 is C1-C25alkyl,
-
- wherein E3 is C1-C10alkyl or C2-C10alkenyl, E4 is C1-C10alkylene, and E5 and E6 independently of one another are C1-C4alkyl, cyclohexyl or methylcyclohexyl, and
- if m1 is 4, E2 is C4-C10alkanetetrayl;
-
- in which
- two of the radicals E7 are —COO—(C1-C20alkyl), and
-
- with E8 having one of the meanings of E1;
-
- in which
- E9 and E10 together form C2-C14alkylene,
- E11 is hydrogen or a group -Z1-COO-Z2,
- Z1 is C2-C14alkylene, and
- Z2 is C1-C24alkyl, and
- E12 has one of the meanings of E1;
-
- wherein
- the radicals E13 independently of one another have one of the meanings of E1,
- the radicals E14 independently of one another are hydrogen or C1-C12alkyl, and
- E15 is C1-C10alkylene or C3-C10alkylidene;
-
- wherein
- the radicals E16 independently of one another have one of the meanings of E1;
-
- in which
- E17 is C1-C24alkyl, and
- E18 has one of the meanings of E1;
-
- in which
-
- wherein E22 has one of the meanings of E1;
-
- wherein
- the radicals E23 independently of one another have one of the meanings of E1,
- and E24 is hydrogen, C1-C12alkyl or C1-C12alkoxy;
-
- wherein
- m2 is 1, 2 or 3,
- E25 has one of the meanings of E1, and
-
- when m2 is 2, E26 is C2-C22alkylene, and
-
- wherein the radicals E27 independently of one another are C2-C12alkylene, and the radicals E28 independently of one another are C1-C12alkyl or C5-C12cycloalkyl;
-
- wherein
- the radicals E29 independently of one another have one of the meanings of E1, and E30 is C2-C22alkylene, C5-C7cycloalkylene, C1-C4alkylenedi(C5-C7cycloalkylene), phenylene or phenylenedi(C1-C4alkylene); or
-
- in which
- E31 is C1-C10alkyl, C5-C12cycloalkyl, C1-C4alkyl-substituted C5-C12cycloalkyl, phenyl or C1-C10alkyl-substituted phenyl,
- E32 is C3-C10alkylene,
- E33 has one of the meanings of E1, and
- m3 is a number from 2 to 6.
- One of the preferred embodiments of this invention relates to stabilizer mixtures wherein the two compounds of component (B) are selected from different classes.
- Examples of component (B) are:
- A compound selected from the class β-1 and a compound selected from the class β-3, β-4, β-5, β-6, β-7, β-8, β-9, β-10 or β-11, preferably the class β-3, β-5, β-6, β-10 or β-11.
- A compound selected from the class β-3 and a compound selected from the class β-4, β-5, β-6, β-7, β-9, β-10 or β-11, preferably β-5, β-6, β-10 or β-11.
- A compound selected from the class β-5 and a compound selected from the class β-6, β-7, β-8, β-9, β-10 or β-11, preferably β-6, β-10 or β-11.
- A compound selected from the class β-6 and a compound selected from the class β-10 or β-11.
- A compound selected from the class β-7 and a compound selected from the class β-8, β-10 or β-11.
- A compound selected from the class β-9 and a compound selected from the class β-10 or β-11.
- A compound selected from the class β-10 and a compound selected from the class β-11.
- Examples of alkyl having up to 25 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl. One of the preferred definitions of A8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 is C1-C4alkyl, especially methyl.
- Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of E1 is octoxy. E24 is preferably C1-C4alkoxy.
- Examples of C5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C5-C8Cycloalkyl, especially cyclohexyl, is preferred.
- C1-C4Alkyl-substituted C5-C12cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
- Examples of C5-C12cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C5-C8Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
- C1-C10Alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl.
- Examples of C7-C9phenylalkyl are benzyl and phenylethyl.
- C7-C9Phenylalkyl which is substituted on the phenyl radical by 1, 2 or 3 C1-C4alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
- Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.
- Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl. C1-C8Alkanoyl, C3-C8alkenyl and benzoyl are preferred. Acetyl and acryloyl are especially preferred.
- Examples of alkylene having up to 22 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
-
- An example of C4-C10alkanetetrayl is 1,2,3,4-butanetetrayl.
- An example of C5-C7cycloalkylene is cyclohexylene.
- An example of C1-C4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.
- An example of phenylenedi(C1-C4alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
- n1, n2, n2* and n4 are preferably a number from 2 to 25, in particular 2 to 20. n3 is preferably a number from 1 to 25, in particular 1 to 20.
- m3 is preferably a number from 2 to 6 or 2 to 5, in particular 2 to 4.
- The compounds described above as components (A) and (B) are essentially known and commercially available. All of them can be prepared by known processes.
- The preparation of the compounds of component (A) is disclosed for example in U.S. Pat. No. 4,233,412, U.S. Pat. No. 4,340,534, WO-A-98/51,690 and EP-A-1,803.
- The preparation of the compounds of component (B) is disclosed for example in U.S. Pat. No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat. No. 4,198,334, U.S. Pat. No. 5,204,473, U.S. Pat. No. 4,619,958, U.S. Pat. No. 4,110,306, U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,689,416, U.S. Pat. No. 4,408,051, SU-A-768,175 (Derwent 88-138,751/20), U.S. Pat. No. 5,049,604, U.S. Pat. No. 4,769,457, U.S. Pat. No. 4,356,307, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,182,390, GB-A-2,269,819, U.S. Pat. No. 4,292,240, U.S. Pat. No. 5,026,849, U.S. Pat. No. 5,071,981, U.S. Pat. No. 4,547,538, U.S. Pat. No. 4,976,889 and U.S. Pat. No. 5,051,458.
- Component (A) is preferably TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) or FERRO AM 806 (RTM).
- The compounds of component (B) are preferably selected from the group consisting of DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31(RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110×128 (RTM), UVINUL 4050 H (RTM), UVASIL 299 LM (RTM) and UVASIL 2000 LM (RTM).
- The meanings of the terminal groups which saturate the free valences in the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-4) and (B-11) depend on the processes used for their preparation. The terminal groups can also be modified after the preparation of the compounds.
-
-
-
- group.
- In the compounds of the formula (A-2-b), the terminal group bonded to the dimethylene radical can be, for example, —OH, and the terminal group bonded to the oxygen can be, for example, hydrogen. The terminal groups can also be polyether radicals.
- In the compounds of the formula (A-4), the end group bonded to the —CH2— residue can be, for example, hydrogen and the end group bonded to the —CH(CO2A7) residue can be, for example, —CH═CH—COOA7.
- In the compounds of the formula (B-11), the terminal group bonded to the silicon atom can be, for example, (E31)3Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(E31)3.
- The compounds of the formula (B-11) can also be in the form of cyclic compounds if m3 is a number from 3 to 6, i.e. the free valences shown in the structural formula then form a direct bond.
- A8 is preferably hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
- E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are preferably hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
- A8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are in particular hydrogen or methyl and E1 additionally is C1-C8alkoxy.
- According to a preferred embodiment
- A1 is hydrogen or methyl,
- A2 is a direct bond or C2-C6alkylene, and
- n1 is a number from 2 to 25;
- n2 and n2* are a number from 2 to 25;
- A3 and A4 independently of one another are hydrogen or C1-C4alkyl, or A3 and A4 together form a C9-C13alkylene group, and
- the variables n3 independently of one another are a number from 1 to 25;
- n4 is a number from 2 to 25,
- A5 and A6 independently of one another are C1-C4alkyl, and
- A7 is C1-C4alkyl or a group of the formula (a-I)
- with the proviso that at least 50% of the radicals A7 are a group of the formula (a-I).
- According to a further preferred embodiment
- m1 is 1, 2 or 4,
- if m1 is 1, E2 is C12-C20alkyl,
- if m1 is 2, E2 is C2-C10alkylene or a group of the formula (b-I)
- E3 is C1-C4alkyl,
- E4 is C1-C6alkylene, and
- E5 and E6 independently of one another are C1-C4alkyl, and
- if m1 is 4, E2 is C4-C8alkanetetrayl;
- two of the radicals E7 are —COO—(C10-C15alkyl), and
- two of the radicals E7 are a group of the formula (b-II);
- E9 and E10 together form C9-C13alkylene,
- E11 is hydrogen or a group -Z1-COO-Z2,
- Z1 is C2-C6alkylene, and
- Z2 is C10-C16alkyl;
- E14 is hydrogen, and
- E15 is C2-C6alkylene or C3-C5alkylidene;
- E17 is C10-C14alkyl;
- E24 is C1-C4alkoxy;
- m2 is 1, 2 or 3,
-
- when m2 is 2, E26 is C2-C6alkylene, and
- when m2 is 3, E26 is a group of the formula (b-IV)
- the radicals E27 independently of one another are C2-C6alkylene, and
- the radicals E28 independently of one another are C1-C4alkyl or C5-C8cycloalkyl;
- E30 is C2-C8alkylene; and
- E31 is C1-C4alkyl,
- E32 is C3-C6alkylene, and
- m3 is a number from 2 to 6.
- A particularly preferred embodiment of this invention relates to a stabilizer mixture wherein
-
-
-
-
- wherein n4 is a number from 2 to 20, and
-
- wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
- and the remaining radicals A7 are ethyl; and
-
-
-
-
-
-
-
-
-
-
-
-
-
- wherein m3 is a number from 2 to 6 and E33 has one of the meanings of E1.
- A particularly preferred embodiment of this invention also relates to a stabilizer mixture wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
- Another preferred embodiment of this invention relates to a stabilizer mixture wherein
- component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20; and
- one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
- A further particularly preferred embodiment of this invention is a stabilizer mixture wherein
- component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20;
- one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen; and
- the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E1 being hydrogen, (B-1-b) with E1 being methyl, (B-1-d) with E1 being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with E12 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with E16 being hydrogen, (B-6-a) with E18 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11-a) with E33 being hydrogen.
- Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products:
- 1. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 765 (RTM)
- 2. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 144 (RTM)
- 3. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 123 (RTM)
- 4. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen
- 5. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+HOSTAVIN N 24 (RTM)
- 6. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+DIACETAM 5 (RTM)
- 7. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 52 (RTM)
- 8. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 57 (RTM)
- 9. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 62 (RTM)
- 10. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 67 (RTM)
- 11. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3034 (RTM)
- 12. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3150 (RTM)
- 13. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3159 (RTM)
- 14. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 15. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVINUL 4049 (RTM)
- 16. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 17. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 18. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SUMISORB TM 61 (RTM)
- 19. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SANDUVOR 3050 (RTM)
- 20. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SANDUVOR PR-31 (RTM)
- 21. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVASIL 299 LM (RTM)
- 22. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVASIL 2000 LM (RTM)
- 23. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 24. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 25. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 26. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+TINUVIN 144 (RTM)
- 27. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+TINUVIN 123 (RTM)
- 28. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen
- 29. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+HOSTAVIN N 24 (RTM)
- 30. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+DIACETAM 5 (RTM)
- 31. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 52 (RTM)
- 32. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 57 (RTM)
- 33. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 62 (RTM)
- 34. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 67 (RTM)
- 35. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3034 (RTM)
- 36. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3150 (RTM)
- 37. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3159 (RTM)
- 38. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 39. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVINUL 4049 (RTM)
- 40. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 41. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 42. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SUMISORB TM 61 (RTM)
- 43. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SANDUVOR 3050 (RTM)
- 44. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SANDUVOR PR-31 (RTM)
- 45. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVASIL 299 LM (RTM)
- 46. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVASIL 2000 LM (RTM)
- 47. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 48. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 49. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 50. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+TINUVIN 123 (RTM)
- 51. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen
- 52. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+HOSTAVIN N 24 (RTM)
- 53. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+DIACETAM 5 (RTM)
- 54. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 52 (RTM)
- 55. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 57 (RTM)
- 56. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 62 (RTM)
- 57. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 67 (RTM)
- 58. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3034 (RTM)
- 59. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3150 (RTM)
- 60. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3159 (RTM)
- 61. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 62. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVINUL 4049 (RTM)
- 63. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 64. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 65. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SUMISORB TM 61 (RTM)
- 66. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SANDUVOR 3050 (RTM)
- 67. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SANDUVOR PR-31 (RTM)
- 68. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVASIL 299 LM (RTM)
- 69. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVASIL 2000 LM (RTM)
- 70. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 71. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 72. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 73. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen
- 74. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+HOSTAVIN N 24 (RTM)
- 75. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+DIACETAM 5 (RTM)
- 76. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 52 (RTM)
- 77. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 57 (RTM)
- 78. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 62 (RTM)
- 79. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 67 (RTM)
- 80. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3034 (RTM)
- 81. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3150 (RTM)
- 82. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3159 (RTM)
- 83. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 84. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVINUL 4049 (RTM)
- 85. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 86. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 87. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SUMISORB TM 61 (RTM)
- 88. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SANDUVOR 3050 (RTM)
- 89. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SANDUVOR PR-31 (RTM)
- 90. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVASIL 299 LM (RTM)
- 91. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVASIL 2000 LM (RTM)
- 92. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 93. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 94. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 95. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+HOSTAVIN N 24 (RTM)
- 96. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+DIACETAM 5 (RTM)
- 97. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+ADK STAB LA 52 (RTM)
- 98. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+ADK STAB LA 57 (RTM)
- 99. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+ADK STAB LA 62 (RTM)
- 100. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+ADK STAB LA 67 (RTM)
- 101. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+GOODRITE UV 3034 (RTM)
- 102. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+GOODRITE UV 3150 (RTM)
- 103. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+GOODRITE UV 3159 (RTM)
- 104. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-9-a) wherein E25 is hydrogen
- 105. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+UVINUL 4049 (RTM)
- 106. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-10-a) wherein E29 is hydrogen
- 107. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
- 108. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+SUMISORB TM 61 (RTM)
- 109. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+SANDUVOR 3050 (RTM)
- 110. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+SANDUVOR PR-31 (RTM)
- 111. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+UVASIL 299 LM (RTM)
- 112. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+UVASIL 2000 LM (RTM)
- 113. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
- 114. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
- 115. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E12 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 116. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+DIACETAM 5 (RTM)
- 117. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 52 (RTM)
- 118. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 57 (RTM)
- 119. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 62 (RTM)
- 120. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 67 (RTM)
- 121. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3034 (RTM)
- 122. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3150 (RTM)
- 123. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3159 (RTM)
- 124. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 125. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVINUL 4049 (RTM)
- 126. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 127. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 128. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SUMISORB TM 61 (RTM)
- 129. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SANDUVOR 3050 (RTM)
- 130. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SANDUVOR PR-31 (RTM)
- 131. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVASIL 299 LM (RTM)
- 132. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVASIL 2000 LM (RTM)
- 133. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 134. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 135. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 136. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 52 (RTM)
- 137. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 57 (RTM)
- 138. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 62 (RTM)
- 139. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 67 (RTM)
- 140. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3034 (RTM)
- 141. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3150 (RTM)
- 142. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3159 (RTM)
- 143. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 144. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVINUL 4049 (RTM)
- 145. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 146. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 147. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SUMISORB TM 61 (RTM)
- 148. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SANDUVOR 3050 (RTM)
- 149. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SANDUVOR PR-31 (RTM)
- 150. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVASIL 299 LM (RTM)
- 151. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVASIL 2000 LM (RTM)
- 152. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 153. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 154. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 155. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 57 (RTM)
- 156. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 62 (RTM)
- 157. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 67 (RTM)
- 158. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3034 (RTM)
- 159. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3150 (RTM)
- 160. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3159 (RTM)
- 161. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 162. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVINUL 4049 (RTM)
- 163. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 164. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 165. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SUMISORB TM 61 (RTM)
- 166. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SANDUVOR 3050 (RTM)
- 167. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SANDUVOR PR-31 (RTM)
- 168. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVASIL 299 LM (RTM)
- 169. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVASIL 2000 LM (RTM)
- 170. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 171. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 172. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 173. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+ADK STAB LA 62 (RTM)
- 174. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+ADK STAB LA 67 (RTM)
- 175. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3034 (RTM)
- 176. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3150 (RTM)
- 177. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3159 (RTM)
- 178. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 179. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVINUL 4049 (RTM)
- 180. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 181. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 182. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SUMISORB TM 61 (RTM)
- 183. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SANDUVOR 3050 (RTM)
- 184. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SANDUVOR PR-31 (RTM)
- 185. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVASIL 299 LM (RTM)
- 186. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVASIL 2000 LM (RTM)
- 187. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 188. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 189. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 190. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+ADK STAB LA 67 (RTM)
- 191. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3034 (RTM)
- 192. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3150 (RTM)
- 193. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3159 (RTM)
- 194. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 195. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVINUL 4049 (RTM)
- 196. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 197. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 198. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SUMISORB TM 61 (RTM)
- 199. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SANDUVOR 3050 (RTM)
- 200. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SANDUVOR PR-31 (RTM)
- 201. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVASIL 299 LM (RTM)
- 202. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVASIL 2000 LM (RTM)
- 203. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 204. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 205. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 206. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3034 (RTM)
- 207. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3150 (RTM)
- 208. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3159 (RTM)
- 209. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 210. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVINUL 4049 (RTM)
- 211. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 212. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 213. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SUMISORB TM 61 (RTM)
- 214. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SANDUVOR 3050 (RTM)
- 215. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SANDUVOR PR-31 (RTM)
- 216. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVASIL 299 LM (RTM)
- 217. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVASIL 2000 LM (RTM)
- 218. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 219. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 220. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 221. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+GOODRITE UV 3150 (RTM)
- 222. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+GOODRITE UV 3159 (RTM)
- 223. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 224. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVINUL 4049 (RTM)
- 225. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 226. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 227. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SUMISORB TM 61 (RTM)
- 228. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SANDUVOR 3050 (RTM)
- 229. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SANDUVOR PR-31 (RTM)
- 230. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVASIL 299 LM (RTM)
- 231. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVASIL 2000 LM (RTM)
- 232. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 233. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 234. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 235. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+GOODRITE UV 3159 (RTM)
- 236. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 237. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVINUL 4049 (RTM)
- 238. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 239. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 240. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SUMISORB TM 61 (RTM)
- 241. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SANDUVOR 3050 (RTM)
- 242. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SANDUVOR PR-31 (RTM)
- 243. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVASIL 299 LM (RTM)
- 244. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVASIL 2000 LM (RTM)
- 245. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 246. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 247. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 248. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen
- 249. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVINUL 4049 (RTM)
- 250. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 251. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 252. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SUMISORB TM 61 (RTM)
- 253. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SANDUVOR 3050 (RTM)
- 254. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SANDUVOR PR-31 (RTM)
- 255. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVASIL 299 LM (RTM)
- 256. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVASIL 2000 LM (RTM)
- 257. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 258. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 259. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 260. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+UVINUL 4049 (RTM)
- 261. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+compound of the formula (B-10-a) wherein E29 is hydrogen
- 262. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
- 263. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+SUMISORB TM 61 (RTM)
- 264. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+SANDUVOR 3050 (RTM)
- 265. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+SANDUVOR PR-31 (RTM)
- 266. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+UVASIL 299 LM (RTM)
- 267. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+UVASIL 2000 LM (RTM)
- 268. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
- 269. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
- 270. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E25 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 271. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen
- 272. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen
- 273. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SUMISORB TM 61 (RTM)
- 274. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SANIDUVOR 3050 (RTM)
- 275. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SANDUVOR PR-31 (RTM)
- 276. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+UVASIL 299 LM (RTM)
- 277. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+UVASIL 2000 LM (RTM)
- 278. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 279. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 280. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 281. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
- 282. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+SUMISORB TM 61 (RTM)
- 283. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+SANDUVOR 3050 (RTM)
- 284. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+SANDUVOR PR-31 (RTM)
- 285. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+UVASIL 299 LM (RTM)
- 286. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+UVASIL 2000 LM (RTM)
- 287. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
- 288. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
- 289. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E29 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 290. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+SUMISORB TM 61 (RTM)
- 291. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+SANBUVOR 3050 (RTM)
- 292. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+SANDUVOR PR-31 (RTM)
- 293. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+UVASIL 299 LM (RTM)
- 294. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+UVASIL 2000 LM (RTM)
- 295. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
- 296. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
- 297. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E1 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 298. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+SANDUVOR 3050 (RTM)
- 299. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+SANDUVOR PR-31 (RTM)
- 300. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+UVASIL 299 LM (RTM)
- 301. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+UVASIL 2000 LM (RTM)
- 302. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 303. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 304. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 305. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+SANDUVOR PR-31 (RTM)
- 306. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+UVASIL 299 LM (RTM)
- 307. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+UVASIL 2000 LM (RTM)
- 308. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 309. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 310. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 311. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+UVASIL 299 LM (RTM)
- 312. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+UVASIL 2000 LM (RTM)
- 313. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 314. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 315. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 316. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 317. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 318. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 319. TINUVIN 622 (RTM)+UVASIL 2600 LM (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen
- 320. TINUVIN 622 (RTM)+UVASIL 2000 LM (RTM)+compound of the formula (B-6-a) wherein E18 is methyl
- 321. TINUVIN 622 (RTM)+UVASIL 2000 LM (RTM)+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 322. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
- 323. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E18 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
- 324. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E18 is methyl+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
-
- wherein n2 and n2* are a number from 2 to 20.
-
-
- and the remaining radicals A7 are ethyl.
- Combinations of particular interest are numbers 1, 4, 7, 8, 12, 13 and 15 to 24, and the corresponding combinations wherein TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b).
- Further combinations of particular interest are numbers 3, 4, 8, 17 and 31.
- The commercial product TINUVIN 622 (RTM) corresponds to the compound of the formula (A-1-a).
- The commercial product TINUVIN 770 (RTM) corresponds to the compound of the formula (B-1-b) wherein E1 is hydrogen.
- The commercial product TINUVIN 765 (RTM) corresponds to the compound of the formula (B-1-b) wherein E1 is methyl.
- The commercial product TINUVIN 123 (RTM) corresponds to the compound of the formula (B-1-b) wherein E1 is octyloxy.
- The commercial product TINUVIN 144 (RTM) corresponds to the compound of the formula (B-1-c) wherein E1 is methyl.
- The commercial product ADK STAB LA 57 (RTM) corresponds to the compound of the formula (B-1-d) wherein E1 is hydrogen.
- The commercial product ADK STAB LA 52 (RTM) corresponds to the compound of the formula (B-1-d) wherein E1 is methyl.
- The commercial product ADK STAB LA 67 (RTM) corresponds to the compound of the formula (B-2-a) wherein E8 is hydrogen.
- The commercial product ADK STAB LA 62 (RTM) corresponds to the compound of the formula (B-2-a) wherein E1 is methyl.
- The commercial product HOSTAVIN N 24 (RTM) corresponds to the compound of the formula (B-3-b) wherein E12 is hydrogen.
- The commercial product SANDUVOR 3050 (RTM) corresponds to the compound of the formula (B-3-b-1) shown below, wherein E12 is hydrogen.
- The commercial product DIACETAM 5 (RTM) corresponds to the compound of the formula (B-4-a) wherein E13 is hydrogen.
- The commercial product SUMISORB TM 61 corresponds to the compound of the formula (B-4-b) wherein E13 is hydrogen.
- The commercial product UVINUL 4049 (RTM) corresponds to the compound of the formula (B-5) wherein E16 is hydrogen.
- The commercial product SANDUVOR PR 31 (RTM) corresponds to the compound of the formula (B-8-a) wherein E23 is methyl.
- The commercial product GOODRITE 3034 (RTM) corresponds to the compound of the formula (B-9-b) wherein E25 is hydrogen.
- The commercial product GOODRITE 3150 (RTM) corresponds to the compound of the formula (B-9-c) wherein E25 is hydrogen.
- The commercial product GOODRITE 3159 (RTM) corresponds to the compound of the formula (B-9-c) wherein E25 is methyl.
- The commercial product UVASIL 299 LM (RTM) or UVASIL 2000 LM (RTM) contains as active ingredient the compound of the formula (B-11-a) wherein R16 is hydrogen.
-
- The stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation. Examples of such organic materials are the following:
- 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
- Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
- a) radical polymerisation (normally under high pressure and at elevated temperature).
- b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
- 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
- 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
- 4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
- 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
- 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
- 7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
- 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
- 9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
- 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrilel butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
- 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
- 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
- 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
- 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
- 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
- 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 619, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
- 17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
- 18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
- 19. Polycarbonates and polyester carbonates.
- 20. Polysulfones, polyether sulfones and polyether ketones.
- 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
- 22. Drying and non-drying alkyd resins.
- 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
- 24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
- 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
- 26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
- 27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
- 28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
- 29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
- 30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
- This invention therefore additionally relates to a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described herein above.
- A further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described herein above.
- The organic material is preferably a synthetic polymer, in particular from one of the above groups. Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer and a polypropylene copolymer are particularly preferred.
- The compounds of components (A) and (B) may be added to the organic material to be stabilized either individually or mixed with one another.
- Each of the compounds of components (A) and (B) may be present in the organic material in an amount of preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material.
- The weight ratio of the components (A):(B) is preferably 10:1 to 1:100, in particular 10:1 to 1:10 or 5:1 to 1:5. Further examples for the weight ratio are also 1:1 to 1:10, for example 1:2 to 1:5.
- The weight ratio of the two components forming component (B) is for example 1:10 to 10:1 or 1:5 to 5:1, preferably 1:2 to 2:1, in particular 1:1.
- The above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent. The components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
- If desired, the compounds of components (A) and (B) can be blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.
- The materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.
- The stabilized material may additionally also contain various conventional additives, for example:
- 1. Antioxidants
- 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.
- 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
- 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
- 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
- 1.5. Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
- 1.6. Alkylidenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-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-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-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(5-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-4hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
- 1.7. O—, N— and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
- 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
- 1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
- 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
- 1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
- 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
- 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
- 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
- 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
- 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
- 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-1, supplied by Uniroyal).
- 1.18. Ascorbic acid (vitamin C)
- 1.19. Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
- 2. UV Absorbers and Light Stabilisers
- 2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;
- where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotraizol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
- 2.2. 2-Hydroxybenzophenones, for example the 4hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.
- 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
- 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-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 the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
- 2.6. Oxamides, for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
- 2.7. 2-(2-Hydroxyphenyl)-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-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-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)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
- 3. Metal deactivators, for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
- 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, dilsodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2′,2′-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
- The following phosphites are especially preferred:
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- 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
- 6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
- 7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
- 8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.
- 9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
- 10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
- 11. Nucleatina agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
- 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
- 13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
- 14. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.
- The weight ratio of the total amount of components (A) and (B) to the total amount of the conventional additives can be, for example, 100:1 to 1:100 or 10:1 to 1:10.
- The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.
- Light Stabilizers Used in the Following Examples 1 and 2:
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- Mixture (A-2):
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- Light Stabilization of Polypropylene Homopolymer Films.
- 100 parts of unstabilized polypropylene powder (melt flow index: 2.4 g/10 minutes at 230° C. and 2160 g) are homogenized at 200° C. for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl}phosphite, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated Table 1. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying).
- Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
- The exposure time (T0.1) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in Table 1. High T0.1 values are desired.
TABLE 1 T0.1 in hours Light stabilizer system in combi- nation with TINUVIN T0.1 622 in hours (RTM) The The amount amount of the of the light light stabilizers stabilizers used is used is 0.075% 0.05% Light stabilizer system each*). each*). Without 185 — TINUVIN 770 (RTM) + TINUVIN 765 (RTM) 1780 3095 TINUVIN 770 (RTM) + TINUVIN 144 (RTM) 1990 2815 TINUVIN 770 (RTM) + TINUVIN 123 (RTM) 1780 2650 TINUVIN 770 (RTM) + HOSTAVIN N 20 2760 3205 (RTM) TINUVIN 770 (RTM) + ADK STAB LA 57 2245 3045 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3034 2440 3570 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3150 2715 3230 (RTM) TINUVIN 770 (RTM) + Compound (B-6-a-1) 1930 3095 TINUVIN 770 (RTM) + Compound (B-6-a-2) 2000 3400 TINUVIN 770 (RTM) + Compound (B-10-a-1) 3510 3940 TINUVIN 770 (RTM) + Compound (B-1-a-1) 1715 3520 TINUVIN 770 (RTM) + SANDUVOR 3050 1630 3040 (RTM) TINUVIN 770 (RTM) + SANDUVOR PR-31 1885 2730 (RTM) HOSTAVIN N 20 (RTM) + ADK STAB LA 57 2485 2765 (RTM) HOSTAVIN N 20 (RTM) + Compound (B-6-a-1) 2625 3010 HOSTAVIN N 20 (RTM) + UVINUL 4049 H 2655 3245 (RTM) HOSTAVIN N 20 (RTM) + Compound (B-1-a-1) 2510 3055 HOSTAVIN N 20 (RTM) + SANDUVOR 2120 3140 PR-31 (RTM) ADK STAB LA 57 (RTM) + TINUVIN 765 2290 2705 (RTM) ADK STAB LA 57 (RTM) + GOODRITE 2305 2930 UV 3150 (RTM) ADK STAB LA 57 (RTM) + Compound 2255 2745 (B-6-a-2) ADK STAB LA 57 (RTM) + UVINUL 4049 H 2400 2735 (RTM) ADK STAB LA 57 (RTM) + SANDUVOR 1670 2655 PR-31 (RTM) GOODRITE UV 3150 (RTM) + Compound 2390 3040 (B-6-a-1) GOODRITE UV 3150 (RTM) + Compound 2155 2670 (B-6-a-2) GOODRITE UV 3150 (RTM) + SANDUVOR 2075 2840 PR-31 (RTM) Compound (B-6-a-1) + TINUVIN 765 (RTM) 2230 3010 Compound (B-6-a-1) + Compound (B-6-a-2) 2235 2980 Compound (B-6-a-1) + UVINUL 4049 H (RTM) 2465 3235 Compound (B-6-a-1) + Compound (B-1-a-1) 2225 2775 Compound (B-10-a-1) + UVINUL 4049 H (RTM) 3430 4055 Compound (B-10-a-1) + SANDUVOR PR-31 2710 3255 (RTM) Compound (B-1-a-1) + TINUVIN 765 (RTM) 2365 3060 Compound (B-1-a-1) + UVINUL 4049 H (RTM) 2475 3205 Compound (B-1-a-1) + SANDUVOR PR-31 1845 2550 (RTM) Compound (B-1-a-1) + Compound (B-6-a-2) 2240 2650 - Light Stabilization of Polypropylene Homopolymer Films.
- 100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g/10 minutes at 230° C. and 2160 g) are homogenized at 200° C. for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl {tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl)phosphite}, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated in Tables 2A to 2H. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying).
- Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
- The exposure time (T0.1) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in the following tables. High T0.1 values are desired.
TABLE 2A T0.1 T0.1 T0.1 in hours in hours in hours Light Light Light stabilizer stabilizer stabilizer system in system in system in combi- combi- combi- nation nation nation with with with TINUVIN TINUVIN TINUVIN 622 622 622 (RTM) (RTM) (RTM) The The The amount amount amount of the of the of the stabilizers stabilizers stabilizers of the of the of the light light light T0.1 stabilizer stabilizer stabilizer in hours system system system The is 0.05% is 0.075% is 0.09% amount each each each of the and the and the and the light amount of amount of amount stabilizers TINUVIN TINUVIN TINUVIN Light used 622 622 622 stabilizer is 0.1% (RTM) is (RTM) is (RTM) is system each*). 0.10%*). 0.05%*). 0.02%*).* Without 300 TINUVIN 770 (RTM) + 4635 7530 7585 6235 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4935 7940 7170 7130 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5105 7455 7030 6890 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 6710 6945 7865 8010 ADK STAB LA 52 (RTM) TINUVIN 770 (RTM) + 5450 7225 7225 7280 ADK STAB LA 57 (RTM) TINUVIN 770 (RTM) + 5915 6700 7190 7025 ADK STAB LA 67 (RTM) TINUVIN 770 (RTM) + 6925 >8340 >8340 7360 GOODRITE UV 3034 (RTM) TINUVIN 770 (RTM) + 6325 7965 7625 7025 GOODRITE UV 3150 (RTM) TINUVIN 770 (RTM) + 6040 7400 7540 7025 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5070 7005 6990 5735 SANDUVOR 3050 (RTM) TINUVIN 770 (RTM) + 5745 7470 6765 6705 SANDUVOR PR-31 (RTM) -
TABLE 2B T0.1 in hours Light stabilizer T0.1 system in combination in hours with Mixture (A-2) The amount The amount of the of the light stabilizers of the light stabilizers stabilizer system is 0.075% used is each and the amount of Light stabilizer system 0.1% each*). Mixture (A-2) is 0.05%*). Without 300 — TINUVIN 770 (RTM) + 4635 6025 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4935 6080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5105 6005 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 5450 6800 ADK STAB LA 57 (RTM) TINUVIN 770 (RTM) + 6925 7735 GOODRITE UV 3034 (RTM) TINUVIN 770 (RTM) + 6530 7335 Compound (B-6-a-2) TINUVIN 770 (RTM) + 6040 6905 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5070 >6495 SANDUVOR 3050 (RTM) -
TABLE 2C T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 315 — TINUVIN 770 (RTM) + 4815 >7260 TINUVIN 765 (RTM) TINUVIN 770 (RTM) + 5695 7145 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4670 7080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5390 6710 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 6655 >7260 ADK STAB LA 52 (RTM) TINUVIN 770 (RTM) + 5040 6760 ADK STAB LA 62 (RTM) TINUVIN 770 (RTM) + 5010 6205 ADK STAB LA 67 (RTM) TINUVIN 770 (RTM) + 5825 >7260 Compound (B-10-a-1) TINUVIN 770 (RTM) + 6125 7215 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5690 >7260 SANDUVOR 3050 (RTM) TINUVIN 770 (RTM) + 5100 6475 SANDUVOR PR-31 (RTM) -
TABLE 2D T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 315 — TINUVIN 765 (RTM) + 4930 7180 TINUVIN 144 (RTM) TINUVIN 765 (RTM) + 4640 >7260 TINUVIN 123 (RTM) TINUVIN 765 (RTM) + 6580 >7260 HOSTAVIN N 20 (RTM) TINUVIN 765 (RTM) + 5325 7040 HOSTAVIN N 24 (RTM) TINUVIN 765 (RTM) + 5605 >7260 ADK STAB LA 52 (RTM) TINUVIN 765 (RTM) + 5360 6905 ADK STAB LA 57 (RTM) TINUVIN 765 (RTM) + 4620 >7260 ADK STAB LA 62 (RTM) TINUVIN 765 (RTM) + 4840 6625 ADK STAB LA 67 (RTM) TINUVIN 765 (RTM) + 6550 >7260 GOODRITE UV 3034 (RTM) TINUVIN 765 (RTM) + 5715 >7260 GOODRITE UV 3150 (RTM) TINUVIN 765 (RTM) + 5105 >7260 Compound (B-6-a-1) TINUVIN 765 (RTM) + 6145 >7260 Compound (B-1-a-1) TINUVIN 765 (RTM) + 5425 >7260 SANDUVOR 3050 (RTM) TINUVIN 765 (RTM) + 4920 6675 SANDUVOR PR-31 (RTM) -
TABLE 2E T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 330 TINUVIN 144 (RTM) + 3185 5765 TINUVIN 123 (RTM) TINUV1N 144 (RTM) + 4295 6150 HOSTAVIN N 20 (RTM) TINUVIN 144 (RTM) + 3725 5720 HOSTAVIN N 24 (RTM) TINUVIN 144 (RTM) + 4195 5635 ADK STAB LA 52 (RTM) TINUVIN 144 (RTM) + 4870 6350 ADK STAB LA 57 (RTM) TINUVIN 144 (RTM) + 2815 5695 ADK STAB LA 62 (RTM) TINUVIN 144 (RTM) + 3910 4940 ADK STAB LA 67 (RTM) TINUVIN 144 (RTM) + 4185 6115 GOODRITE UV 3034 (RTM) TINUVIN 144 (RTM) + 4290 5725 GOODRITE UV 3150 (RTM) TINUVIN 144 (RTM) + 5515 6565 Compound (B-6-a-1) TINUVIN 144 (RTM) + 5100 6810 Compound (B-6-a-2) TINUVIN 144 (RTM) + 5380 6585 Compound (B-10-a-1) TINUVIN 144 (RTM) + 5470 6305 Compound (B-1-a-1) TINUVIN 144 (RTM) + 4030 5200 SANDUVOR 3050 (RTM) TINUVIN 144 (RTM) + 3105 5890 SANDUVOR PR-31 (RTM) -
TABLE 2F T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 330 TINUVIN 123 (RTM) + 4455 5715 HOSTAVIN N 20 (RTM) TINUVIN 123 (RTM) + 3490 5265 HOSTAVIN N 24 (RTM) TINUVIN 123 (RTM) + 4620 5610 ADK STAB LA 52 (RTM) TINUVIN 123 (RTM) + 4275 5670 ADK STAB LA 57 (RTM) TINUVIN 123 (RTM) + 3380 5185 ADK STAB LA 62 (RTM) TINUVIN 123 (RTM) + 3470 5355 ADK STAB LA 67 (RTM) TINUVIN 123 (RTM) + 4520 >6280 GOODRITE UV 3034 (RTM) TINUVIN 123 (RTM) + 4260 5635 GOODRITE UV 3150 (RTM) TINUVIN 123 (RTM) + 4760 6145 Compound (B-6-a-1) TINUVIN 123 (RTM) + 5115 6365 Compound (B-6-a-2) TINUVIN 123 (RTM) + 5785 6700 Compound (B-10-a-1) TINUVIN 123 (RTM) + 4345 6115 Compound (B-1-a-1) TINUVIN 123 (RTM) + 3650 5040 SANDUVOR 3050 (RTM) TINUVIN 123 (RTM) + 3655 5390 SANDUVOR PR-31 (RTM) TINUVIN 123 (RTM) + 4305 5205 Compound (B-7-1) -
TABLE 2G T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 325 HOSTAVIN N 20 (RTM) + 3695 4565 HOSTAVIN N 24 (RTM) HOSTAVIN N 20 (RTM) + 4375 5525 ADK STAB LA 52 (RTM) HOSTAVIN N 20 (RTM) + 4485 5535 ADK STAB LA 57 (RTM) HOSTAVIN N 20 (RTM) + 3810 5315 ADK STAB LA 62 (RTM) HOSTAVIN N 20 (RTM) + 3655 5045 ADK STAB LA 67 (RTM) HOSTAVIN N 20 (RTM) + 5005 5610 GOODRITE UV 3034 (RTM) HOSTAVIN N 20 (RTM) + 3950 5050 GOODRITE UV 3150 (RTM) HOSTAVIN N 20 (RTM) + 5025 >5890 Compound (B-6-a-1) HOSTAVIN N 20 (RTM) + 5465 >5890 Compound (B-6-a-2) HOSTAVIN N 20 (RTM) + 5405 >5890 Compound (B-10-a-1) HOSTAVIN N 20 (RTM) + 5410 >5890 Compound (B-1-a-1) HOSTAVIN N 20 (RTM) + 3985 5090 SANDUVOR 3050 (RTM) HOSTAVIN N 20 (RTM) + 4085 5255 SANDUVOR PR-31 (RTM) HOSTAVIN N 20 (RTM) + 4200 5220 Compound (B-7-1) -
TABLE 2H T0.1 in hours Light stabilizer T0.1 system in combination in hours with TINUVIN 622 (RTM) The amount The amount of of the the stabilizers of the light the light stabilizer system stabilizers is 0.075% each and the used is amount of TINUVIN 622 Light stabilizer system 0.1% each*). (RTM) is 0.05%*). Without 325 ADK STAB LA 57 (RTM) + 4035 5020 HOSTAVIN N 24 (RTM) ADK STAB LA 57 (RTM) + 3855 4985 ADK STAB LA 52 (RTM) ADK STAB LA 57 (RTM) + 4320 4890 GOODRITE UV 3150 (RTM) ADK STAB LA 57 (RTM) + 3970 4430 SANDUVOR PR-31 (RTM) ADK STAB LA 57 (RTM) + 3765 4475 Compound (B-7-1)
Claims (17)
1. A stabilizer mixture containing the components (A) and (B) wherein
component (A) is
a compound of the formula (A-1)
wherein
A1 is hydrogen or C1-C4alkyl,
A2 is a direct bond or C1-C10alkylene, and
n1 is a number from 2 to 50;
at least one compound of the formulae (A-2-a) and (A-2-b)
a compound of the formula (A-3)
wherein
A3 and A4 independently of one another are hydrogen or C1-C8alkyl, or A3 and A4 together form a C2-C14alkylene group, and
the variables n3 independently of one another are a number from 1 to 50; or
a compound of the formula (A-4)
wherein
n4 is a number from 2 to 50,
A5 is hydrogen or C1-C4alkyl,
the radicals A6 and A7 independently of one another are C1-C4alkyl or a group of the formula (a-I)
wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
with the proviso that at least 50% of the radicals A7 are a group of the formula (a-I); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
with the proviso that components (A) and (B) are different.
2. A stabilizer mixture according to claim 1 wherein the two different compounds of component (B) are selected from the group consisting of the classes
β-1) a compound of the formula (B-1)
in which
E1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
m1 is 1, 2 or 4,
if m1 is 1, E2 is C1-C25alkyl,
if m1 is 2, E2 is C1-C14alkylene or a group of the formula (b-I)
wherein E3 is C1-C10alkyl or C2-C10alkenyl, E4 is C1-C10alkylene, and E5 and E6 independently of one another are C1-C4alkyl, cyclohexyl or methylcyclohexyl, and
if m1 is 4, E2 is C4-C10alkanetetrayl;
β-2) a compound of the formula (B-2)
in which
two of the radicals E7 are —COO—(C1-C20alkyl), and
two of the radicals E7 are a group of the formula (b-II)
with E8 having one of the meanings of E1;
β-3) a compound of the formula (B-3)
in which
E9 and E10 together form C2-C14alkylene,
E11 is hydrogen or a group -Z1-COO-Z2,
Z1 is C2-C14alkylene, and
Z2 is C1-C24alkyl, and
E12 has one of the meanings of E1;
β-4) a compound of the formula (B-4)
wherein
the radicals E13 independently of one another have one of the meanings of E1, the radicals E14 independently of one another are hydrogen or C1-C12alkyl, and
E15 is C1-C10alkylene or C3-C10alkylidene;
β-5) a compound of the formula (B-5)
wherein
the radicals E16 independently of one another have one of the meanings of E1;
β-6) a compound of the formula (B-6)
in which
E17 is C1-C24alkyl, and
E18 has one of the meanings of E1;
β-7) a compound of the formula (B-7)
in which
E19, E20 and E21 independently of one another are a group of the formula (b-III)
wherein E22 has one of the meanings of E1;
β-8) a compound of the formula (B-8)
wherein
the radicals E23 independently of one another have one of the meanings of E1, and E24 is hydrogen, C1-C12alkyl or C1-C12alkoxy;
β-9) a compound of the formula (B-9)
wherein
m2 is 1, 2 or 3,
E25 has one of the meanings of E1, and
when m2 is 1, E26 is a group
when m2 is 2, E26 is C2-C22alkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
wherein the radicals E27 independently of one another are C2-C12alkylene, and the radicals E28 independently of one another are C1-C12alkyl or C5-C12cycloalkyl;
β-10) a compound of the formula (B-10)
wherein
the radicals E29 independently of one another have one of the meanings of E1, and E30 is C2-C22alkylene, C5C7cycloalkylene, C1-C4alkylenedi(C5-C7cycloalkylene), phenylene or phenylenedi(C1-C4alkylene); or
β-11) a compound of the formula (B-11)
in which
E31 is C1-C10alkyl, C5-C12cycloalkyl, C1-C4alkyl-subsbtuted C5-C12cycloalkyl, phenyl or C1-C10alkyl-substituted phenyl,
E32 is C3-C10alkylene,
E33 has one of the meanings of E1, and
m3 is a number from 2 to 6.
3. A stabilizer mixture according to claim 1 wherein
A1 is hydrogen or methyl,
A2 is a direct bond or C2-C6alkylene, and
n1 is a number from 2 to 25;
n2 and n2* are a number from 2 to 25;
A3 and A4 independently of one another are hydrogen or C1-C4alkyl, or A3 and A4 together form a C9-C13alkylene group, and
the variables n3 independently of one another are a number from 1 to 25;
n4 is a number from 2 to 25,
A5 and A6 independently of one another are C1-C4alkyl, and
A7 is C1-C4alkyl or a group of the formula (a-I)
with the proviso that at least 50% of the radicals A7 are a group of the formula (a-I).
4. A stabilizer mixture according to claim 2 wherein
m1 is 1, 2 or 4,
if m1 is 1, E2 is C12-C20alkyl,
if m1 is 2, E2 is C2-C10alkylene or a group of the formula (b-I)
E3 is C1-C4alkyl,
E4 is C1-C6alkylene, and
E5 and E6 independently of one another are C1-C4alkyl, and
if m1 is 4, E2 is C4-C8alkanetetrayl;
two of the radicals E7 are —COO—(C10-C15alkyl), and
two of the radicals E7 are a group of the formula (b-II);
E9 and E10 together form C9-C13alkylene,
E11 is hydrogen or a group -Z1-COO-Z2,
Z1 is C2-C6alkylene, and
Z2 is C10-C16alkyl;
E14 is hydrogen, and
E15 is C2-C6alkylene or C3-C5alkylidene;
E17 is C10-C14alkyl;
E24 is C1-C4alkoxy;
m2 is 1, 2 or 3,
when m2 is 1, E26 is a group
when m2 is 2, E26 is C2-C6alkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
the radicals E27 independently of one another are C2-C6alkylene, and
the radicals E28 independently of one another are C1-C4alkyl or C5-C8cycloalkyl;
E30 is C2-C8alkylene; and
E31 is C1-C4alkyl,
E32 is C3-C6alkylene, and
m3 is a number from 2 to 6.
5. A stabilizer mixture according to claim 1 wherein
component (A) is a compound of the formula (A-1-a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
wherein n1 is a number from 2 to 20;
wherein n2 and n2* are a number from 2 to 20;
wherein the variables n3 independently of one another are a number from 1 to 20;
wherein n4 is a number from 2 to 20, and at least 50% of the radicals A7 are a group of the formula (a-I)
wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
and the remaining radicals A7 are ethyl; and
component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11-a);
wherein E1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl;
in which two of the radicals E7 are —COO—C13H27 and
two of the radicals E7 are
and E8 has one of the meanings of E1;
wherein E12 has one of the meanings of E1;
wherein E13 has one of the meanings of E1;
wherein E16 has one of the meanings of E1;
wherein E18 has one of the meanings of E1;
in which E19, E20 and E21 independently of one another are a group of the formula (b-III)
wherein E22 has one of the meanings of E1;
wherein E23 has one of the meanings of E1;
wherein E25 has one of the meanings of E1;
wherein E29 has one of the meanings of E1;
wherein m3 is a number from 2 to 6 and E33 has one of the meanings of E1.
6. A stabilizer mixture according to claim 1 wherein A8 is hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
7. A stabilizer mixture according to claim 2 wherein E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
8. A stabilizer mixture according to claim 5 wherein A8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are hydrogen or methyl and E1 additionally is C1-C8alkoxy.
9. A stabilizer mixture according to claim 5 wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
10. A stabilizer mixture according to claim 5 wherein
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20; and
one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
11. A stabilizer mixture according to claim 5 wherein component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20;
one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen; and
the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E1 being hydrogen, (B-1-b) with E1 being methyl, (B-1-d) with E1 being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with E12 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with E16 being hydrogen, (B-6-a) with E18 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11-a) with E33 being hydrogen.
12. A stabilizer mixture according to claim 5 wherein
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-b) wherein E1 is octyloxy; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-3-a) wherein E12 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-d) wherein E1 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-a) wherein E1 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is methyl, and
component (C) is a compound of the formula (B-1-d) wherein E1 is methyl.
13. A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to claim 1 .
14. A composition according to claim 13 wherein the organic material is a synthetic polymer.
15. A composition according to claim 13 wherein the organic material is a polyolefin.
16. A composition according to claim 13 wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.
17. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material a stabilizer mixture according to claim 1.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US11/052,714 US20050143500A1 (en) | 2000-05-31 | 2005-01-19 | Stabilizer mixtures |
US11/498,351 US20060270764A1 (en) | 2000-05-31 | 2006-08-03 | Stabilizer mixtures |
US12/317,014 US20090105379A1 (en) | 2000-05-31 | 2008-12-18 | Stabilizer mixtures |
US12/607,102 US7820744B2 (en) | 2000-05-31 | 2009-10-28 | Stabilizer mixtures |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00810482 | 2000-05-31 | ||
EP00810482.0 | 2000-05-31 | ||
EP00810600 | 2000-07-10 | ||
EP00810600.7 | 2000-07-10 | ||
PCT/EP2001/005865 WO2001092398A2 (en) | 2000-05-31 | 2001-05-22 | Stabilizer mixtures |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/052,714 Continuation US20050143500A1 (en) | 2000-05-31 | 2005-01-19 | Stabilizer mixtures |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030197151A1 true US20030197151A1 (en) | 2003-10-23 |
Family
ID=26073903
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/276,120 Abandoned US20030197151A1 (en) | 2000-05-31 | 2001-05-22 | Stabilizer mixtures |
US11/052,714 Abandoned US20050143500A1 (en) | 2000-05-31 | 2005-01-19 | Stabilizer mixtures |
US11/498,351 Abandoned US20060270764A1 (en) | 2000-05-31 | 2006-08-03 | Stabilizer mixtures |
US12/317,014 Abandoned US20090105379A1 (en) | 2000-05-31 | 2008-12-18 | Stabilizer mixtures |
US12/607,102 Expired - Fee Related US7820744B2 (en) | 2000-05-31 | 2009-10-28 | Stabilizer mixtures |
Family Applications After (4)
Application Number | Title | Priority Date | Filing Date |
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US11/052,714 Abandoned US20050143500A1 (en) | 2000-05-31 | 2005-01-19 | Stabilizer mixtures |
US11/498,351 Abandoned US20060270764A1 (en) | 2000-05-31 | 2006-08-03 | Stabilizer mixtures |
US12/317,014 Abandoned US20090105379A1 (en) | 2000-05-31 | 2008-12-18 | Stabilizer mixtures |
US12/607,102 Expired - Fee Related US7820744B2 (en) | 2000-05-31 | 2009-10-28 | Stabilizer mixtures |
Country Status (16)
Country | Link |
---|---|
US (5) | US20030197151A1 (en) |
JP (1) | JP5498638B2 (en) |
KR (1) | KR100786239B1 (en) |
CN (1) | CN1235958C (en) |
AU (2) | AU6601001A (en) |
BE (1) | BE1014207A3 (en) |
BR (1) | BR0111290B1 (en) |
CA (1) | CA2408093A1 (en) |
DE (1) | DE10196264T1 (en) |
ES (1) | ES2199696B1 (en) |
FR (1) | FR2809740B1 (en) |
GB (1) | GB2378950B (en) |
IT (1) | IT1324894B (en) |
MX (1) | MX286036B (en) |
NL (1) | NL1018186C2 (en) |
WO (1) | WO2001092398A2 (en) |
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EP1564253A1 (en) * | 2004-02-17 | 2005-08-17 | DSM IP Assets B.V. | Unsaturated polyester resins or vinyl ester resin compositions |
EP1564254A1 (en) * | 2004-02-17 | 2005-08-17 | DSM IP Assets B.V. | Unsaturated polyester resing or vinyl ester resin compositions |
US20060124904A1 (en) * | 2002-04-12 | 2006-06-15 | Francois Gugumus | Stabilizer mixtures |
US8366822B2 (en) | 2011-06-20 | 2013-02-05 | Dow Global Technologies Llc | Cementitious tile adhesives and method of applying the same to a tile substrate |
US9062143B2 (en) | 2008-02-08 | 2015-06-23 | Dow Global Technologies Llc | Water-redispersible polymer powder |
US20170306133A1 (en) * | 2014-12-02 | 2017-10-26 | Nuc Corporation | Crosslinkable resin composition and electric wire/cable |
WO2018013181A1 (en) | 2016-07-13 | 2018-01-18 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing mixture of antioxidants |
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SA116370295B1 (en) * | 2015-02-20 | 2016-12-06 | باسف اس اى | Light stabilized polyolefin films, tapes and monofilaments |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060124904A1 (en) * | 2002-04-12 | 2006-06-15 | Francois Gugumus | Stabilizer mixtures |
US7595008B2 (en) | 2002-04-12 | 2009-09-29 | Ciba Specialty Chemicals Corporation | Stabilizer mixtures |
EP1564253A1 (en) * | 2004-02-17 | 2005-08-17 | DSM IP Assets B.V. | Unsaturated polyester resins or vinyl ester resin compositions |
EP1564254A1 (en) * | 2004-02-17 | 2005-08-17 | DSM IP Assets B.V. | Unsaturated polyester resing or vinyl ester resin compositions |
WO2005078019A1 (en) * | 2004-02-17 | 2005-08-25 | Dsm Ip Assets B.V. | Unsaturated polyester resins or vinyl ester resin compositions |
WO2005078020A1 (en) * | 2004-02-17 | 2005-08-25 | Dsm Ip Assets B.V. | Unsaturated polyester resins or vinyl resin compositions |
US9062143B2 (en) | 2008-02-08 | 2015-06-23 | Dow Global Technologies Llc | Water-redispersible polymer powder |
US8366822B2 (en) | 2011-06-20 | 2013-02-05 | Dow Global Technologies Llc | Cementitious tile adhesives and method of applying the same to a tile substrate |
US20170306133A1 (en) * | 2014-12-02 | 2017-10-26 | Nuc Corporation | Crosslinkable resin composition and electric wire/cable |
WO2018013181A1 (en) | 2016-07-13 | 2018-01-18 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing mixture of antioxidants |
US10077410B2 (en) | 2016-07-13 | 2018-09-18 | Chevron Oronite Company Llc | Synergistic lubricating oil composition containing mixture of antioxidants |
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