Title of Invention | POLYMER COMPOSITION STABILIZED AGAINST OXIDATIVE, THERMAL OR LIGHT-INDUCED DEGRADATION |
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Abstract | The present invention relates to a polymer composition stabilized against thermal or light-induced degradation, and b) at least a compound of the formula I wherein R1 and R2 are each independently of one another hydrogen or C1-C8alkyl, R3 and R4 are each independently of one another C1-C12 alkyl, and R5 is C1-C7alkyl. |
Full Text | Stabilization of Synthetic Polymers The present invention relates to compositions comprising a synthetic polymer subject to oxi¬dative, thermal or light-induced degradation, especially polyolefins, polyether polyol or poly-urethane, and as stabilizer a specific group of compounds of the benzofuran-2-on6 type. The use of compounds of the benzofuran-2-one type as stabilizers for synthetic polymers is known, for example, from WO-A-80/01566 or US 5,516,920. The known stabilizers do not satisfy in every respect the high requirements which a stabilizer is required to meet, especially with regard to shelf life, water absorption, sensitivity to hydro¬lysis, in-process stabilization, color properties, volatility, migration behaviour, compatibility apd improvement in protection against light. As a result there continues to be a need for effective stabilizers for synthetic polymers that are sensitive to oxidative, thermal and/or light-induced degradation. EP-A-0 871 066 discloses the use of a specific group of compounds of the benzofuran-2-one type as DOX scavengers in color photographic materiais. It has now been found that a specific group of compounds of the benzofuran-2-one type disclosed in EP-A-0 871 066 is particularly suitable as a stabilizer for synthetic polymers which are sensitive to oxidative, thermal or light-induced degradation. The present invention therefore provides composiUons comprising a) a synthetic polymer subject to oxidative, thermal or light-induced degradation, and b) at least a compound of the formula 1 R, and R2 are each independently of one another hydrogen or C1-C6alkyI, R3 and R4 are each independently of one another CrCijalkyl, and R5 is C1-C7alkyl. Alkyl having up to 12 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, seC1-butyi, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetra-methylbuty! (tert-octyl), 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexy!, 1,1,3-trimethyi-hexyi, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl or dodecyt. One of the preferred definitions for Ri and R2 is, for example, C1-C6alkyI, especially C1-C6lkyl, e.g. tert-butyl. Preferably, R3 and R4 are C4-C12alkyl, especially C4-C10alkyl, e.g. C6alkyl. A pre¬ferred definition of R5 is C1-C4alkyl, especially d-Cgalkyl, e.g. methyl. Preferred compounds of the formula I are those wherein R, and R2 are each independently of one another hydrogen or C1-C4alkyl, R3 and R4 are each independently 0I one anotiier C4-C10alkyl, and R5 is C1-C4alkyl. Further preferred compounds of the formula I are those wherein R3 and R4 are tert-octyl. 01 special interest is the compound of the formula 1 wherein Ri and Ra are hydrogen, R3 and R4 are tert-octyl, and R5 is methyl. The synthesis of the compounds of the formula 1 is for example disclosed in EP-A-0 871 066. The compounds of the formula 1 are suitable for stabilizing synthetic polymers against oxida¬tive, thermal or light-induced degradation. Examples of such materials are: 1. Polymers of monooielins and diolelins, for example polypropylene, polyisobutylene, po-lybut-1-ene, pory-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cyclooleflns, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HOPE), high density and high molecular weight polyethylene (HDPE-HIV1W), high density and ultrahigh molecular weight polyethylene (HDPE-UHfvlW), 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, prefe¬rably 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 n- or cr-coordinated. These metal comptexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) 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 la. Ma and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyi ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Zlegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with poiyisobutyiene, polypropylene with poiyelhyiene (tor example PP/HDPE, PPA-DPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). - - 3. Copolymers of monoolefins and diolefins with each other or with other vinyl uionomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propyiene/isobutylene copolymers, ethylene/but-l-ene copolymers, ethyiene/hexene copo¬lymers, ethylene/methylpentene copolymers, ettiylene/heptene copolymers, ethyiene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbomene like COC), ethylene/1-olefins copolymers, where the 1-olefin is gene¬rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi-nylcyclohexene copolymers, ethylene/alkyi acrylate copolymers, ethylene/alkyi methacrylate copolymers, ethylene/vinyl acetate copolymers or ethyl ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyctopentadiene or ethylidene-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethy-lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal-kylene/carbon monoxide copolymers and mixtures tinereof with other polymers, for example polyamides. 4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of poiyalkylenes and starch. Homopolymers and copolymers from 1.} - 4.) may have any stereostructure including syndio-tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Slereoblock polymers are also included. 5. Polystyrene, poly(p-methylstyrene), paly{a-methyistyrene). 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, a-methylstyrene, all isomers of viny! toluene, especially p-vinylto!uene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndlotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Ste-reoblock polymers are also included. - - 6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selec¬ted from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, malmides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu-tadiene, styrene/acrylonitriie, styrene/ethylene (inlerpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhy¬dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copo¬lymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro-pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty-rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy-lene/styrene. 6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylefhylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH). 6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.). Homopolymers and copolymers may have any stereostructure including syndiotactic, isotaC1-tic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included. 7. Graft copolymers of vinyl aromatic monomers such as styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry-ionitrile copolymers; styrene and acrylonitrile (or methaorylonitrile) 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 acrytates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene lerpolymers; styrene and acrylonitrile on polyalkyi acrylates or polyalkyi 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 a,P-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylafes, polyacrylamides and polyacryloni- Iriles, impact-modified with butyl acrylale. 10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu¬rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyi acrylate or acrylonitrile/vinyl halide copolymers or acry¬lonitrile/ alkyl methacry late/butadiene tsrpolymers. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace-tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrai, polyallyl phthaiats or poiyallyl melamine; as well as their copolymers with olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy¬lene 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 polybutadi-enes on the one hand and aliphatic or aromatiC1- polyisocyanates on the other, as well as precursors thereof. 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic adds or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6. 6/10,6/9,6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xyiene diamine and adipic acid; polyamides prepared from hexamethyienedi-amine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poiy-2,4,4,-trlmethylhexamethylene terephthalamide or poly-m-phenylene iso-phthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, tonomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethyiene glycol, polypropylene glycol or polytetramethytene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Poiyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantolns and polybenzimldazoles. 18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph¬thalate, poly-1,4-dimethylolcyciohexane 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. Polyketones. 21. Polysulfones, polyether sulfones and polyether ketones. 22. 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 re¬sins and melamine/formaldehyde resins. 23. Drying and non-drying alkyd resins. 24. 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 flammabiiity. 25. Crosslinkable acryiic resins derived from substituted acrylates, for example epoxy acry-lates, urethane acrylates or polyester acrylates. 26. Alltyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, Isocyanates, isocyanurates, polyisocyanates or epoxy resins. 27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic giycidyl 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. 28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDIvl 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/IVIBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC. The synthetic polymers to be protected are preferably thermoplastic polymers, especially polyolefins, polyether polyols or polyurethanes, in particular polyethylene and polypropylene or copolymers thereof with mono- and diolefins. The compounds of the formula I are likewise used for polyurethane production, especially for preparing flexible polyurethane foams. In this context the novercomposltions and the pro¬ducts produced therefrom are effectively protected against degradation. In particular, scor¬ching during foam production is avoided. Polyurethane foamers may post-add phospites as plaslicizers such as diphenyl isodecyl phosphite (DPDP), phenyl diisodecyl phosphite (PDDP)"to the base stabilized polyether polyols at the mixing head prior to the foaming in relative high concentrations (up to 1.5 % by weight based on the polyether polyol). In the presence of this high amount of phosphites the formed polyurethane foams show ar • '- sired discoloration (pinking and/or yellowing). However, in the presence of the compounds of the formula I the polyurethane foams are white. The polyurethanes are obtained, for example, by reacting polyethers, polyesters and poly-butadienes which contain terminal hydroxyi groups with aliphatic or aromatic polyisocya-nates. Polyethers having terminal hydroxyi groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydro-furan, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF3, or by addition reaction of these epoxides, alone or as a mixture or in succession, with star¬ting components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines, tor example ethylene glycol, propylene 1,3- and 1,2-glycol, trimethyloipropane, 4,4'-dlhydroxydiphenyipropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers are also suitable in accordance with the invention. In many cases preference is given to those polyethers which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) contain primary OH groups. Furthermore, polyethers modified by vinyl polymers, as are formed, for example, by polymerizing styrepe and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups. These compounds generally have molecular weights of 40 and are polyhydroxy compounds, especially compounds containing from two to eight hydroxyi groups, especially those of molecular weight from 800 to 10 000, preferably from 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4, hydroxyi groups, as are known for the preparation of homogeneous polyurethanes and cellular polyurethanes. It is of course possible to employ mixtures of the above compounds containing at least two isocyanate-reactive hydrogen atoms, in particular with a molecular weight of 400 - 1Q 000. Suitable polyisocyanates are aliphatic, cyctoaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanat6, cyclohexane 1,3- and -1,4-diisocyanate and also any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethy!-5-isocyanatomethylcyclohexane, 2,4-. arid 2,6-hexahydrotolylene diisocyanate and also any desired mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethanedilsocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and also any desired mix¬tures of these isomers, diphenylmethane 2,4'- and/or -4,4'-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane 4,4',4"-triisocyanate, polyphenyl-polymethylene polyisocya¬nates as are obtained by aniline-formaldehyde condensation followed by phosgenization, m-and p-isocyanatophenylsulfonyl isocyanates, perch(orinafed aryl polyisocyanates, polyiso¬cyanates containing carbodiimide groups, polyisocyanates containing aKophanate groups, polyisocyanates containing- isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acylated urea groups, poiyisocyanates containing biuret groups, polyisocyanates containing ester groups, reaction products of the abovementioned isocyanates with acetals, and polyisocyanates containing polymeric fatty acid radicals. If is also possible to employ the isocyanate group-containing distillation residues, 'as they are or dissolved in one or more of the abovementioned polyisocyanates, which are obtained in the course of the industrial preparation of isocyanates. It is additionally possible to use any desired mixtures of the abovementioned polyisocyanates. Particular preference is given in general to the polyisocyanates which are readily obtainable industrially, for example 2,4- and 2,6-tolyiene diisocyanate and any desired mixtures of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates as prepared by aniline-formalde¬hyde condensation followed by phosgenization {"crude MDI"), and polyisocyanates contai¬ning carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups ("modified polyisocyanates"). Particular emphasis is to be placed on the action of the compounds of the formula I against thermal and oxidative degradation, especially under thermal stress as occurs during the pro¬cessing of thermoplastics. The compounds of the formula I are therefore outstandingly sui¬table for use as in-process stabilizers. The compounds of the formula I.are preferably added to the synthetic polymer to be stabi¬lized in an amount of from 0.0005 to 10 %, in particular from 0.001 to 2 %, for example from 0.01 to 2 %, based on the weight of the synthetic polymer to be stabilized. In addition to components (a) and (b) the novel compositions may comprise further costabiii-zers (additives) such as, for example, the following: 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-buty[-4-n-buty[phenol, 2,6-di-tert-bu-tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexy()-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricycioh6xylphenol, 2,6-di-tert-butyl-4-meth-oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-m6thy(undeC1-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadeC1-1'-yl)phenol, 2,4-dimethyi-6-{1'-m6thyltrideC1-r-yl)phenol and mixtures there¬of. 1.2. Alkvlthiomethvlphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-diocty(thiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 1.3. Hvdroquinones and alkylated hydroquinones. for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyioxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-c!i-tert-butyt-4-hydroxyanisQle, 3,5-di-tert-bu-tyl-4-hydroxyanisole, 3,5-d[-tert-butyl-4-hydroxyphenyl stearate, bis{3,5-di-tert-butyl-4-hy-droxyphenyl) adipate. 1.4. Tocopherols, for example a-tocopherol, |3-tocopherol, Y-tocopheroi, 5-tocopherol and mixtures thereof (vitamin E). 1.5. Hvdroxviated thiodiphenvi ethers, for example 2,2'-lhiobis(6-tert-butyl-4-methy!phenoO, 2,2'-thiobis(4-ootylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-seC1-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide. ■1.6. AlkvlidenebisDhenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)- phenol], 2,2'-methylenebis{4-methyl-6-cyciohexylphenoi), 2,2'-methylenebis(6-nonyi-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-efhylidenebis(4,6-di-tsrt-butyl-phenol), 2,2'-ethylidenebis(6-lert-butyl-4-isobutylphenot), 2,2'-methylenebis[6-(ct-methylben-zyl}-4-nonylphenol], 2,2'-methylenebis[6-{a,a-dimethylbenzyi)-4-nonylph8nol], 4,4'-methy-lenebis(2,6-dl-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-lris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-buty(-4-hydroxy-2-methylphenyi)-3-n-dodecy[mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], ' bis(3-tert-butyl-4-hydroxy-5-methyl-phenyi)dicyclopenta-diene, bts[2-(3'-tert-butyl-2'-hydroxy-5'-methyibenzyl)-6-tert-butyi-4-m6thylphenyi]terephtha-late, 1,1-bis-{3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe-ny!)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. 0-. N- and S-benzvl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-d[hydroxydi-benzyl ether, octadecyi-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris{3,5-di-tert-butyi-4-hydroxybenzyl)amine, bis{4-tert-butyl-3-hydroxy-2,6-dlmethylbenzyl)dithioterephthalate, bis(3,5-dl-tert-buty(-4-hydroxy-benzyl)sulfide, iSQQctyl-3,5-di-tert-butyl-4-hydrQxybenzylmercaptoacetate. 1.8. Hvdroxvbenzvlated malonates. for example diDctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy-droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecyimercaptoethyl-2,2-bis{3,5-di-tert-butyl-4-hydroxybenzyl)maionate, bisI4-(1,1,3,3-te-tramethylbutyl)phenyl]-2,2-bis{3,5-di-tert-butyl-4-hydroxybenzyl)malonate. 1.9. Aromatic hydroxvbenzvl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethy!benzene, 1,4-bis(3,5-dl-tert-butyl-4-hydroxyben2yl)-2,3,5,6-tetrame-thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyben2yl)phenol. 1.10. Triazine compounds, for example 2,4-bis(octylm6rcapto)-6-(3,5-di-tert-butyi-4-hydroxy- anilinp)-1,3,5-triazine, . 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri- azine, 2-octylmercapto-4,6-b!s{3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-lris- (3,5-di-tert-butyi-4-hydroxyphenoxy}-1,2,3-triazlne, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- 2yl)isocya"nurate, 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-tr!s(3,5-dl-tert-butyl-4-hydroxy-plienylpropionyl)-hexahydro-1,3.5-triazine, 1.3,5-tris(3,5-dicyclohexyl-4-hydroxybenzy()iso-cyanurate. 1.11. BenzvlphosDhonates. for example dim6thyl-2,5-di-tert-butyl-4-hydroxyben2ylphospho-nate, diethyi-3,5-di-tert-butyi-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy' droxybenzylphosphonate, dioctadecyJ-5-tert-butyl-4-hydroxy-3-methyibenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminoohenols. for example 4-hydroxylaurantilde, 4-hydroxystearaniiide, octyl N-(3,5-di-tert-buty!-4-hydroxyphenyl)carbamate. 1.13. Esters of p-{3,5-di-tert-butvl-4-hvdroxvphenvHpropionic acid with mono- or poiyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyi glycol, thiodiethylene glycol, diethy-lene glycol, triethylene glycol, pentaerythritol, trisChydroxyethy!}isocyanurate. N,N'-bis(hy-droxyetbyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of B-f5-tert-butvl-4-hvdroxv-3-methvlphenvl)propionic acid with mono- or poiy¬hydric Edcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi¬ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyi glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyOisocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, thmethyl-olpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyi)propionyloxy}-1,1-dimethyiethyl]-2,4,8.10-tetraoxaspirD[5.5]: undecane. 1.15- Esters of B-(3.5-dicvclohexvl-4-hvdroxvphenYl)propionic acid with mono- or poiyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanedlol, ethylene glycol, 1,2-propanediol, neopentyi glycol, thiodiethylene glycol, diethylene glycol, tri¬ethylene glycol, pentaerythritol, tris{hydroxyethyl}isocyanurate, N,N'-bis{hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyloipropane, 4-hy-droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. . _ 1.16. Esters of 3.5-di-tert-butvl-4-hvdrQxvphenvl acetic acid with mono- or polyhydric alco¬hols, e.g. with methanol, ethanoi, octanol, octadecanoi, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 -propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrltol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl}ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-' drQxyn:iethyl-1-phospha-2,6,7-trioxab!cyclo[2.2.2lQCtane. 1-17. Amides of B-f3.5-di-tert-butvl-4-hvdroxyphenyl) propionic acide.q. N,N'-bis(3,5-di-tert-butvl-4-hydroxyphenylprDpionyt)hexametl-iylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenyIpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-drazide, N,N'-bis[2-{3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethy[]oxamide (Nau-gard®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-seC1-bu-tyl-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'-dicy-clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dlmethylbutyl)-N'-phe-ny|.p.phenylenediamine, N-(1-methylhepty()-N'-phenyl-p-phenylenediamine, N-cyc!ohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diph©nylamine, N,N'-dimethyl-N,N'-di-seC1-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl-amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-l-naphthylamine, N-phenyl-2-naph-thylamine, octylated diphenylamine, tor example p,p'-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol, 4-butyrylamlnophenot, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoyfaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino-methylphenot, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',NMetra-methyl-4,4'-diaminodiphenylmethane, 1,2-bis[C2-methylphenyt)amino]ethane, 1,2-bis(phenyt-amino)prppane, (o-tolyl)biguanide, bisE4-(1',3'-dimethylbutyl)phenyl]amine, lert-octylated H-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyi/tert-octyidiphenyt-amines. a mixture of mono- and dialkylated ncnyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenyiamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dlhydro-3,3-dimethy|-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-a!!ylphenothiazine, N,N,N',N'-tetraphenyt-1,4-diaminobut-2-en6. 2. UV absorbers and light stabili?ers 2.1. 2-f2'-HvdrQxvphenvl)benzotriazQles. for example 2-{2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotnazote, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethytbutyl)phenyl)benzotriazoie, 2-{3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazo(e, 2-(3'-tert-butyl-2'-hydroxy-5'-methyfphe- nyl)-5-chlorobenzotriazo(e, 2-(3'-seC1-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotria2ole, 2-(2'- hydroxy-4'-octyloxypheny!)benzotria2ole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotrJazole, 2-(3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl)phenyl)-5-chloroben20triazoie, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)caitonylethyI]-2'-hydroxyphenyl)-5-chlorobenzotna2ole, 2-(3'-tert-butyi-2'-hydroxy-5'-(2- m6thoxycarbonylethyl)phenyl)-5-GhlorobenzQtriazole, 2-{3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbony[ethyl)phenyl}benzotriazQle, 2-{3'-tert-butyl-2'-hydroxy-5'-{2-octyloxycarbonyl- ethyl)pheny|)benzotriazole, 2-(3'-tert-butyl-5'-[2-{2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyi)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbony!ethyl)phenylbenzotriazole, 2,2'-methylenebisl4-(i, 1,3,3- lelramelhylbutyl)-6-benzotria20te-2-ylphenol]; the transesterrtication product of 2-[3'-tert-bu- ty!-5'-(2-methoxycarbonylethyl)-2'-hydroxypheny!l-2H-benzotriazole with polyethylene glycol 300; [R-CHJCH—COO-CHCHj- , Where R = 3'-tert-butyl-4'-hydroxy-5'-2H-berizot!-i- azol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl}-5'-(a,a-dimethy[benzyl)pheny!]ben-zotriazole. 2.2. 2-HvdrowbenzoDhenones. for example the 4-hydroxy, 4-methoxy, 4-DCtyloxy, 4-decyl- oxy, 4-dodecylGxy, 4-benzyloxy, 4i2-,4'-trihydroxy and 2'-hydroxy-4,4'-dimefhoxy derivatives. 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyiphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyi resorctnol, bis(4-lert-butyiben- zoyOresorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tetl-butyl-4-hydroxybenzo-ate, hexadecyl 3,5-di-tert-butyl-4.hydroxybenzoate, octadecyl 3,5-di-t6rt-butyi-4-hydroxyben-zoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate. 2.4. Acrvlates. for example ethyl a-cyano-p,|3-dlphenylacrylate, isooctyl a-cyano-p,p-diphe-nylacrylate, methyl a-C6rbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinna-mate, butyl a-cyano-g-methyl-p-methoxycinnamate, methyl a-C6rbomethoxy-p-methoxycin-namate and N-(3-C6rbomethoxy-3-cyanovinyt)-2-methylfndoline. 2.5. Nickel comoounds. for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethyl-butyOphenol], 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 monoalkyi esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nicke! complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe-nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyi-5-hydroxypyrazole, with or with¬out additional ligands. 2.6. Stericallv hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl}sebacate, bis(2,2,6,6-tetramethyt-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyi-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethy!-4-piperi-dyi) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethy()-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic aoid, linear or cyclic condensates of-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris{2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetra-methyl-4-piperidy!)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrame-thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl-oxy-2.2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sucC1-nate, linear or cyciic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and 4-morpho(ino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chlorD-4,6-bis{4-n-butylamino-2,2,6,6-tetramethyipiperldyl)-1,3,5-triazine and 1,2-bis(3-aminopropyiamino)-ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1.3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetrame- thyl-1,3,S-tria2aspiro[4,5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr-roiidine-2,5-dione, 3-dodecyl-1-{1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyIoxy-2,2,6,6-tetrametfiylpiperidrne, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethyIenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-tria2ine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-tri-chloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine {CAS Reg. No.-[136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichioro-1,3,5-triarine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine {CAS Reg. No. [192268-64-7]); N-(2,2;6,6'letramethyM-piperidyl)-n-dodecyisuccinimide, N'{1.2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di-a2a-4-oxo-spiro[4,5Idecane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospirQ-[4,5]decane and epichlorohydrin, 1,1 -bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbony()-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetrame-tliy(-4-pjperidyl)hexamethyienediamine, a diester of 4-methoxymethylenemal6nic acid with 1,2,2,6,6-pentamethyi-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-{2,2,6,6-tetramethyl-4-piperidyl)]siloxan6, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidme or 1,2,2,6,6-p6ntam6thyl-4-aminopiperidine. 2.7. Oxamides. for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxaniiide, 2,2'-dioctyioxy-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'-ethoxani[ide and its mixture with 2-ethoxy-2'-6thyl-5,4'-di-tert-butoxanil!de, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8. 2-(2-Hvdroxvphenvn-1.3.5-tria2!nes. 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-tria2ine, 2,4-bis(2-hydroxy-4-propyi-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-dimethyiphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-trideGyloxypheny[)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-{2-hydroxy'3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyi)-1,3,5-triazine, 2-[2-hydroxy-4-{2-hydroxy-3-octyloxypropyloxy)phenyi]-4,6-bis(2,4-dimethyl)-1,3,5-tria2ine, 2-[4-(dodecyioxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylpheny!)- "1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis{2,4-dimethyl- pheny()-1,3,5-!riazine, 2-(2-hydroxy-4-hexyloxy)pheny(-4,6-diphenyl-1,3,5-triazine, 2-{2-hy-droxy-4-melhoxyphenyi)-4,6-diphenyl-1,3,5-tria2ine, 2,4,6-tris[2-hydroxy-4-{3-butoxy-2-hy-droxypropoxy)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-dimethylpheny!)-1,3,5-triazine. 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylai-N*-salicy!oyl liydrazine, N,N'-bis(salicyioyl) hydrazine, N,N'-bis(3,5-di-t6rt-butyi-4-hydrDxyphenytprDpionyt)lnydra2ine, 3-saiicyloy(amino-1,2,4-triazo[e, bis(ben2ylidene)oxa(y( dihydrazide, oxanilide, isophthaloyi dihydrazide, sebacoyi bisphenylhydrazide, N.N'-diacetyiadipoyI dihydrazide, N,N'-bis(sa(icyl-Qyl)Qxalyi dihydrazide, N,N'-bis(sa(iGyloyl)thiopropionyl dihydrazide. 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyi phosphites, phenyldiaikyi phosptiites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos¬phite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-buty!phenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyi)pentaerythritol diphosphite, bis(2,4-di-cumylphenyOpentaerythritol diphosphite, bis[2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, brs(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea-ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butyiphenyl) 4,4'-biphenylene diphosphonite, 6-Jsooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis{2,4-di-tert-butyl-6-melhy)phenyi)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)6thyl pl-iosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dloxaphosphocin, 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'-te-tra-tert-butyl-1,V-biph6nyi-2,2'-diyl)phosphit6. 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane. 5. Hvdroxvlamines. for example N,N-di':--nzythydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhy: viamine, N,N-ditetradecymydroxyiamine, N,N-dihexadecylhydroxylamine, N,N-dioctaaecyihydroxylamine, N-hexadecyl-N-octadecylhydrox-ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones. for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methy(nltrone. N-octyl-alpha-heptylnitrone, N-!auryl-alpha-undecylnitrone, . N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al-pha-heptadecylnitrone, N-ocatadecy(-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyI-amine derived from hydrogenated tallow amine. 7. Thiosvnergists. for example dilauryl thiodipropionate or distearyl thiodipropionate. 8. Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamale, dioctadecyl disulfide, pentaerythritol te{rakis(p-dodecyl mercapto) prop ionate. 9. Polvamide stabilisers, lor example copper salts in combination with iodides and/or phos¬phorus 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. Nucleating 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-butyl benzoic 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(paramethyl-dibenzylidene)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, car¬bon 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. 4,325,863;' U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-{2-ac8toxyethoxy)- phenyl]-5,7-di-tert-butyibenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]- benzofuran-2-one, 3,3'-bis[5,7-di-tert-bufyf-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyi-3-(4-ethoxyphenyObsnzofuran-2-one, 3-(4-acetoxy-3,5-dimethylph6nyi)-5,7- di-tert-butyibenzofuran-2-one, 3-(3,5-dimethy!-4-pivaloyloxyphenyi)-5,7-di-tert-butylbenzo- furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-Qne, 3-(2,3-dimethylphe- nyl)-5,7-dl-tert-butylbenzofuran-2-one. The cosfabilizers are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the synthetic polymer to be stabilized. Preferred further additives are phenolic antioxidants, light-stabilizers and/or processing stabi¬lizers. Preferred further additives for the stabilization of polyurethanes are phenolic antioxi¬dants and/or amino antioxidants of the secondary amine type (aminic antioxidants, item 1.19) and/or phosphites or phosphonites (item 4). Of special interest is a stabilizer mixture comprising Irganox 1135 [RTM, see footnote d) at the end of Table 2], Irganox 5057 [RTM, see footnote c) at the end of Table 2] and a com¬pound of the formula I wherein Ri and R2 are hydrogen, R* and Ra are tert-octyl and R5 is methyl [compound (102), see footnote f) at the end of Table 2]. Preferably the ratio by weight of Irganox 1135; Irganox 5057: compound (102) is for example 100 : 1 : 0.01 to 1 :1 : 10. A mixture of 10 : 3 : 1 will be commercially available as Irgastab PUR 67 [RTM, Ciba Specialty Chemicals Inc.]. Also of Interest is a stabilizer mixture comprising Irganox 1135 [RTM, see footnote d) at the end of Table 2], Irgafos 68 [RTM, bis(2,4-di-tert-butyl-6-methylph8nyl)ethyl phosphite] and a compound of the formula I wherein Ri and R2 are hydrogen, R4 and R4 are' tert-octyl and R5 is methyl [compound (102), see footnote f) at the end of Table 2]. The ratio by weight of Ir-ganox 1135 : Irgafos 68 : compound (102) is for example 100 ; 1 : 0.01 to 1 : 1 ; 10. A stabi¬lizer mixture of 7 : 1 : 1 wiii be commercially available as Irgastab PUR 68 [RTM, Ciba Spe¬cialty Chemicals Inc.] The fillers and reinforcing agents (item 12 in the list), for example tatc, calcium carbonate, mica or kaolin, are added to the polyolefins in concentrations, for example, of from 0.01 to 40 %, based on the overall weight of the polyolefins to be stabilized. The fillers and reinforcing agents (item 12 in the list), for example metal hydroxides, espe¬cially aluminium hydroxide or magnesium hydroxide, are added to the polyolefins in concen¬trations, for example, of from 0.01 to 60 %, based on the overall weight of the polyolefins to be stabilized. Carbon black as filler is added to the polyolefins in concentrations, judiciously, of from 0.01 to 5 %, based on the overall weight of the polyolefins to be stabilized. Glass fibers as reinforcing agents are added to the polyolefins In concentrations, judiciously, of from 0.01 to 20 %, based on the overall weight of the polyolefins to be stabilized. Further preferred compositions comprise in addition to components (a) and (b) further addi¬tives as well, especially alkaline earth, metal salts of higher fatty acids, for example calcium stearate. As a conventional stabilizer combination for processing synthetic polymers, for example po¬lyolefins, to form corresponding mouldings, the combination of a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phosphonite is recommended. De¬pending on the particular substrate and process, however, many polyolefin processors are forced to operate processes in the high-temperature region above about 280°C. By virtue of the incorporation of the compounds of the formula 1, which Is specially suitable for high-tem¬perature applications, in particular in the temperature range above 300°C, industrial mate¬rials and mouldings, based for.instance on high-density polyethylene, for example pipes and their technical variants (fittings), can be produced at a greater rate and with fewer rejects. Another advantage of the compounds of the formula I is that it can be employed in very small amounts. This leads to a reduction in the overall concentration of antioxidant relative to conventional stabilizer mixtures. Thus the use of a low concentration of the compounds of the formula I allow/s a reduction in the overall concentration of stabilizer by about a third in polyolefins, ior example, which simultaneously represent an economic advantage. ■ Incorporation of the compounds of the formula I and, if desired, further additives into the syn--thetic polymers is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the synthetic polymer, if appro¬priate with subsequent slow evaporation of the solvent. The compounds of the formula I can also be added to the synthetic polymers to be stabilized in the form of a masterbatch contai¬ning them, for example, in a concentration of 2.5 to 25% by weight. The compounds of the formula I can also be added before or during polymerisation or before crosslinklng. The compounds of the formula I, with or without further additives, can be incorporated in pure form or encapsulated in waxes, oiis or polymers into the synthetic polymer that is to be stabilized. The compounds of the formula I, with or without further additives, can also be sprayed onto the synthetic polymer that is to be stabilized. It is able to dilute other additives (for example the conventional additives indicated atiove) or their melts so that they too can be sprayed together with these additives onto the polymer that is to be stabilized. Addition by spraying on during the deactivation of the polymerization catalysts Is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation. In the case o1 spherically polymerized polyolefins it may, for example, be advantageous to apply the compounds of the formula I, with or without other additives, by spraying. The materials stabilized in this way can be employed in a wide variety of forms, for example as foams, films, fibres, tapes, moulding compositions, as profiles or as binders for coating materials, especially powder coatings, adhesives or putties. The polyolefins stabilized in this way can likewise be employed in a wide variety of forms, especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks. The preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm. As already mentioned, thermoplastic polymers are protected with particular advantage. Attention should be drawn above all in this context to the outstanding activity of the com¬pounds of the formula i as in-process stabilizer (heat stabilizer). For this purpose the com¬pounds of the formula 1 are advantageously added to the synthetic polymer prior to or during its processing. However, other polymers too (for example elastomers) or lubricants or hy-d'raulic fluids can be stabilized against degradation, for example light-induced or thermooxi-dative degradation. Elastomers can be taken from the above listing of possible synthetic polymers. The lubricants and hydraulic fluids in question are based, for example, on mineral oils or synthetic oils or on mixtures thereof. The lubricants are familiar to the skilled person in the art and are described in the relevant technical literature, for example in Dieter Klamann, "Schmierstoffe und verwandte Produkte" (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" (Dr. Alfred Huthig-Verlag, Heidelberg, 1974) and in "Ullmanns Enzyklopadie der technischen Chemie", Vol.13, pages 85-94 (Verlag Chenrie, Weinheim, 1977). The present invention also relates to a process for stabilizing a synthetic polymer against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto at least a compound of the formula I. A preferred embodiment of the present invention is therefore the use of the compounds of the formula I as stabilizers, especially in-process stabilizer (thermal stabilizer), for synthetic polymers, especially thermoplastic polymers, against oxidative, thermal or light-induced de¬gradation. The examples which follow illustrate the invention in more detail. Parts and percentages are by weight. Example 1: Preparation of polyether/polyurethane soft foams as well as the stabilization thereof. 2 g (0.025 %, based on the poiyol) of a stabilizer according to Table 1 is dissolved in 8 kg of a polyether poiyol, Lupranol 2045 (RTM) (trifunctional polyetfier poiyol having phmary hydroxy} groups; hydroxy! number 35 mg KOH/g, water content less than 0.1 %, acid number less than 0.1 mg KOH/g) which contains 6 g of Irganox 5057 (RTM) [see footnote c) at the end of Table 2] and 4 g of Irganox 1135 (RTM) [see footnote d) at the end of Table 2]. 520 g of a solution consisting of 120 g Tecostab (RTM) (polysilicone supplied by Goldschmidt, Ger¬many], and 6.4 g diazabicyclooctane (amine catalyst) are added and the reaction mixture is stirred vigorously for 60 seconds at 100 rpm. 14.4 g of tin octoate and 120 g (1.5 %, based on the poiyol) of diphenyl isodecy! phosphite (DPDP) is then added and the reaction mixture is again stirred vigorously for 60 seconds at 100 rpm. With vigorous stirring, 5.11 kg of an isocyanate [Lupranat TSO (RTM), supplied by BASF; toluylene-2,4- and toluyien6-2,6-diiso-cyanate mixture] are then added immediately and the mixture is poured into a lined mould and the exothermic temperature is measured during foaming to a foam block. The foam blocks are cooled and stored at room temperature for 24 hours. The next day the foams are cut. The color of the foam blocks is determined visually. The whiter the foam the better is the foam stabilized, it has to be noted ttiat this effect is oniy visible on iarge foaming scale (for example 1 m foam. The obsen/atlon of this effect Is difficult on a lab scale. The results are summarized in Table 1. Example 2: Preparation of ABS (Acrylonitrile-Butadiene-Styrene) as well as the stabilization thereof. 833g of Acrytonitrile-butadiene-styrene graft polymer [Baymod 60A (RTM), Bayer Corp.], 1667g of styrene-acrylonitriie copolymer [Luslran 32 (RTM), Bayer Corp.], 26.25 g of N,N'-etfiytenedi(stearamide), 1.496g of Irganox 1076 [(RTM), n-octadecyl 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, 0,057% based on polymer], 2.993 g of Irgafos 168 [(RTM), tris-(2,4-di-tert-butylphenyJ) phosphite, 0.113% based on polymer] and 0.788 g of a'stabilizer according to Table 2 (0,030% based on polymer) were mixed together on a tumbling barrel mixer dunng 15 hours. The resulting dry-blend was then compounded on twin-screw-extru¬der (Berstorff 46D, at 220°C, 110 rpm and 12 kg/h) and, after drying for 3h at 80°C, injection molded on an Engel HL65 Injection Molder at 2400 (cycle time: 35,8 s; injection speed: 25 mm/s; mold temperature: GCC) to give natural ABS plaques of the dimension 67 x 64 x 2 mm. The initial color of these ABS plaques was measured, then the plaques were exposed to ac¬celerated weathering in a Weather-0-Meter ATLAS Ci 65 for 1000 hours under the following conditions: Irradiation 0.35 W/m at 340nm; Borosilicate inner and outer filter; Black Panel Temperature: 63°C; no dark phase; 60% relative humidity and dry cycle (no rain). The yel¬lowness index (Yl) is determined according to DIN 6167. Low Yl values denote little discolo¬ration, high Yl values high discoloration of the samples. The less discoloration, the more effective the stabilizer. The results are summarized in Table 2. a) Comparison examples. b) Example according to the invention. c) Irganox 5057 (RTM) (Ciba Specialty Chemicals) is a secondary amine antioxidant and is a technical mixture, obtained by reaction of diphenylamine with diisobutylene, comprising a') 3 % of diphenylamine; b'} 14 % of 4-tert-butyldiphenylamine; c') 30 % of compounds of the group i) 4-tert-oGtyldlphenylamine, ii) 4,4'-di-tert-butyldiphenyiarnine, iii) 2,4,4'-tris-tert-butyldiphenylamine; d') 29 % of the compounds of the group i) 4-tert-butyl-4'-tert-octyidiphenylamine, ii) 0,0'-, m,m'- or p,p'-di-tert-octyldiphenylamine, iii) 2,4-di-tert-butyi-4'-tert-octyldiphenylamine; e') 24 % of the compounds of the group i) 4,4'-di-tert-octyldiphenylamine and ii) 2,4-di-tert-octyl-4'-tert-butyldiphenylamine. What is claimed is: 1. A composition comprising a) a synthetic polymer subject to oxidative, thermal or light-induced degradation, and b) at least a compound of the formula I R1 and R2 are each independently of one another hydrogen or C1-C6alkyl, R3 and R4 are each independently of one another C1-C12alkyI, and R5 is C1-C7alkyl. 2. A composition according to claim 1, wherein R1 and R2 are each independently of one another hydrogen or C1-C4alkyl, Ra and R4 are each independently of one another C4-C10alkyI, and R5 is C1-C4alkyl. 3. A composition according to claim 1, wherein R3 and R4 are tert-octyl. 4. A composition according to claim 1, R1 and R2 are hydrogen, R3 and R4 are tert-octyl, and Rs is methyl. 5. A composition according to claim 1, comprising as component (a) a thermoplastic poly¬mer. 6. A compcsiticn according to claim 1, comprising as component (a) a pciyclefin, pciyether poiyol cr polyurethane. 7. A composition according to claim 1, wherein component (b) is present in an amount of 0.0005 to 10 % based on the weight of component (a). |
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0671-mas-2002 correspondnece-others.pdf
0671-mas-2002 correspondnece-po.pdf
0671-mas-2002 descritpion(complete).pdf
Patent Number | 235282 | |||||||||
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Indian Patent Application Number | 671/MAS/2002 | |||||||||
PG Journal Number | 30/2009 | |||||||||
Publication Date | 24-Jul-2009 | |||||||||
Grant Date | 30-Jun-2009 | |||||||||
Date of Filing | 09-Sep-2002 | |||||||||
Name of Patentee | CIBA HOLDING INC. | |||||||||
Applicant Address | KLYBECKSTRASSE 141, 4057 BASEL, | |||||||||
Inventors:
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PCT International Classification Number | C08K5/00 | |||||||||
PCT International Application Number | N/A | |||||||||
PCT International Filing date | ||||||||||
PCT Conventions:
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