MXPA97003907A - Mixtures of acid sterils polialquilpiperidin-4-il dicarboxilico, stabilizers for materialsorgani - Google Patents

Abstract

The present invention relates to a mixture containing two different compounds of the formula (I): wherein n is an integer from 2 to 22 and R is hydrogen, alkyl having from 1 to 8 carbon atoms, -O-, -OH, -NO, -CH2CN, alkoxy with 1 to 18 carbon atoms, cycloalkoxy with 5 to 12 carbon atoms, alkenyl with 3 to 6 carbon atoms, alkynyl with 3 to 6 carbon atoms, acyl with 1 to 8 carbon atoms or phenylalkyl with 7 a 9 carbon atoms unsubstituted or substituted in phenyl by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, the proportion by weight of the two compounds is 1:20 to 20: 1, is useful as a stabilizer for organic materials against degradation induced by light, heat or oxidation

Description

ACID MIXTURES OF POLYALQUILPIPERIDIN-4-IL DICARBOXYLIC, STABILIZERS FOR ORGANIC MATERIALS The present invention relates to a mixture1 containing two different esters of polyalkylopiperidin-4-yl dicarboxylic acid, to the organic material stabilized with the aid of this mixture against degradation induced by light, heat or oxidation and the corresponding use of the mixture to stabilize an organic material. The use of various esters of polyalkylpiperidin-4-yl dicarboxylic acid - as single compounds or in mixtures for stabilizing organic materials for example is described in US Pat. US-A-028 645, US-A-4 461 898 and US-A-4 419 472, EP-A-146 878 and GB-A-2 202 853. The present invention relates to a stabilizing mixture containing two different compounds of the formula (I) wherein n is an integer from 2 to 22 and R is hydrogen, alkyl having 1 to 8 carbon atoms, -O, -OH, -NO, -CH2CN, alkoxy with 1 to 18 carbon atoms, cycloalkoxy with 5 to 12 carbon atoms, alkenyl with 3 to 6 carbon atoms, alkynyl with 3 to 6 carbon atoms, acyl with 1 to 8 carbon atoms or phenylalkyl with 7 to 9 carbon atoms, substituted or unsubstituted in the phenyl for 1, 2 or 3 alkyls with 1 to 4 carbon atoms; the weight ratio of the two compounds is 1:20 to 20: 1. Examples of alkyl with 1 to 8 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl and t-octyl. . Examples of alkoxy having 1 to 18 carbon atoms are ethoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, ieopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Alkoxy with 1 to 8 carbon atoms, heptoxy and octoxy are particularly preferred. Examples of cycloalkyl with 5 to 12 carbon atoms are cyclopentoxy, cyclohexoxi, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Cycloalkyl with 5 to 8 carbon atoms, cyclopentoxy and cyclohexoxi are particularly preferred. Examples of alkenyl having 3 to 6 carbon atoms are allyl, 2-methylallyl, butenyl and hexenyl. The carbon atom connected to nitrogen is preferably saturated.

An example of alkinyl with 3 to 6 carbon atoms is 2-propynyl. Examples of acyl with 1 to 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. Alkanoyl with 1 to 8 carbon atoms and benzoyl are preferred. Acetyl is especially preferred. Examples of phenylalkyl with 7 to 9 carbon atoms which is unsubstituted or substituted in the phenyl by 1, 2 or 3 alkyls with 1 to 8 carbon atoms are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and 2-phenylethyl. Benzyl is preferred. The variable n of preference is an integer from 2 to 10, in particular an integer from 2 to 8, for example 2 to 4 or 4 to 8. The weight ratio of the two different compounds of the formula (I) present in the stabilizing mixture can be 1:20 to 20: 1, preferably it is 1:15 to 15: 1, for example 1:10 to 10: 1, 1: 8 to 8: 1, 1: 6 to 6: 1, 1 : 5 to 5: 1, 1: 4 to 4: 1 or 1: 3 to 3: 1. When the stabilizer mixture additionally contains a third compound of the formula (I), the weight ratio of the compound in the total amount of the other two compounds of the formula (I) can be 1:20 to 20: 1, preferably 1. : 15 to 15: 1, for example 1:10 to 10: 1, 1: 8 to 8: 1, 1: 6 to 6: 1, 1: 5 to 5: 1, 1: 4 to 4: 1 or 1 : 3 to 3: 1.

A preferred embodiment of the present invention relates to a stabilizing mixture wherein the two compounds of the formula (I) differ only in the variable n. A further preferred embodiment of the present invention relates to a mixture wherein the two compounds of the formula (I) differ in the variable n and the difference between the two values of n is 1, 2, 3, 4, or 5. particular interest are the following stabilizing mixtures: - A mixture, wherein the variable n of a compound of the formula (I) is 3 and the variable n of the other compound of the formula (I) is 4 to 8. - A mixture, wherein the variable n of a compound of the formula (I) is 4 and the variable n of the other compound of the formula (I) is 7 or 8. - A mixture, where the variable n of a compound of the formula (I) is 7 and the variable n of the other compound of the formula (I) is 8. Preference is also given to a stabilizing mixture wherein the variable n of a compound of the formula (I) is two, and the variable n of another compound of the formula (I) is 3.; the mixture additionally contains a third compound of the formula (I) with n which is 4.

Of interest is an additional stabilizing mixture wherein the 2 compounds of the formula (I) differ only in the meaning of the radical R. R is preferably hydrogen, alkyl with 1 to 4 carbon atoms, -OH, alkoxy with 1 to 8. carbon atoms, cycloalkoxy with 5 to 8 carbon atoms, allyl, benzyl, acetyl or acryloyl, in particular hydrogen or methyl. The stabilizing mixtures of the compounds of the formula (I) can be prepared analogously to known methods of esterification or transesterification by reacting for example a piperidinol of the formula (II) with a mixture of esters of organic dicarboxylic acid of the formula (III) II fl HO C (CH,); C OH (III) or its derivatives. Suitable dicarboxylic acid derivatives are for example chlorides or lower alkyl esters such as methyl ester or an ethyl ester. When acid chlorides are used in the reaction as derivatives of the dicarboxylic acid esters, it is convenient to add an acid acceptor, for example an amine such as pyridine or triethylamine, in the amount of at least two equivalents with respect to the chlorides of acid. When the reaction is carried out as a transesterification of a piperidinol of the formula (II) with a mixture of dicarboxylic acid esters of the formula (III), usual transesterification catalysts are added to the reaction mixture, for example a base organic or an inorganic base such as LiNH2, LiOMe, KOH, Li-tert-butylate, a ter-amylate (for example Na-ter-amylate) and the like or Le-acids such as dibutyl tin oxide, tris [isopropylate] of Al, tris [sec-butylate] of Al, tetra [isopropylate] of Ti or tetra [sec-propylate] of Ti. The necessary dicarboxylic acid mixtures can be obtained by adding the commercially available dicarboxylic acids. Of particular interest is the use of commercially available dicarboxylic acid mixtures such as "Dicarbonsáuregemisch destilliert" (= Distillate of dicarboxylic acid mixture) ex RBASF or mixtures of dicarboxylic acid ester, for example RDBE, RDBE2 and RDBE3 of RDu Pont.

It is also possible to first prepare the simple compounds of the formula (I) which are subsequently mixed in the desired weight ratio. The stabilizing mixtures according to the present invention are very effective in improving the resistance to light, heat and oxidation of organic materials. These materials, for example, can be oils, fats, cosmetic waxes or biocides. Of particular interest is its use in polymeric materials such as plastics, rubbers and paints. Specific examples of organic materials that can be stabilized are: 1. Polymers of onoolefins and diolefins, for example polypropylene, polyisobutylene, polybutyl-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefin polymers, for example of cyclopentene or norbonene, polyethylene (which can optionally be interlaced), for example high density polyethylene (HDPE), high density polyethylene and high molecular weight (HDPE-HM), high density polyethylene and ultra high molecular weight (HDPE-UHM), medium density polyethylene (MDPE), low density polyethylene (LLDPE), linear low density polyethylene (LDPE), branched low density polyethylene (BLDPE).

Polyolefins, ie the monolefin polymers exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially by the following: a) radical polymerization (normally at high pressure and at elevated temperature). b) catalytic polymerization, using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or HIV 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 which may be p- or s-coordinated. These metal complexes can be in the free form or fixed in substrates, typically in activated magnesium chloride, titanium chloride (111), alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or additional activators can be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides, or metal alkyl oxanes, metals are elements of the groups, Ha and / or Illa of the Periodic Table. The activators can be conveniently modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Styard Oil Indiana, Ziegler (-Natta), TNZ (Du Pont), 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 onoolefins and diolefins with each other or with other vinyl monomers, for example, copolymers of ethylene / propylene, linear low density polyethylene (LLDPE) and their mixtures with low density polyethylene (LDPE), propylene copolymers / but-1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers ethylene / ethylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers , copolymers of isobutylene / isoprene, copolymers of ethylene / alkyl acrylate, copolymers of ethylene / alkyl methacrylate, copolymers of ethylene / vinyl acetate, and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as ethylene terpolymers with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and blends of these copolymers with each other and with polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate (EVA) copolymers, LDPE / ethylene-acrylic acid (EM) copolymers, LLDPE / EVA, LLDPE / EM and alternating or random copolymers of polyalkylene / carbon monoxide and their mixtures with other polymers, for example polyamides. 4. Hydrocarbon resins (for example from 5 to 9 carbon atoms) including their hydrogenated modifications (for example tackifying agents) and mixtures of polyalkylenes and starch. 5.- Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). 6.- Copolymers of styrene or -methylstyrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, e sti r ene / but adi ene / al qu y ac rila te, styrene / butadiene / alkylmethacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate, * mixtures with high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or a terpolymer-ethylene / propylene / diene; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. 7. Styrene or α-methylstyrene graft copolymers, for example styrene in polybutadiene, styrene in polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methyl methacrylate in polybutadiene; styrene and maleic anhydride in polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; styrene and maleimide in polybutadiene; styrene and alkyl acrylates or methacrylates in polybutadiene; styrene and acrylonitrile in ethylene / propylene / diene terpolymers; styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers as well as their mixtures with the copolymers listed under 6), for example mixtures of copolymers 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 sulfochlorinated polyethylene, copolymers of ethylene, and chlorinated ethylene, epichlorohydrin, homo- and co-polymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate. 9. Polymers derived from acids, β-unsaturated and their derivatives such as polyacrylates and polymethacrylates; poly ethyl methacrylates, polyacrylates and polyacrylonitriles, modified against impact with butyl acrylate. 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl ethacrylate / butadiene terpolymers. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as its copolymers with olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers. 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulphides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from polyethers terminated in hydroxyl, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors. 16. Polyamides and copolyamides derived from diaraines and dicarboxylic acids and / or from aminocarboxylic acids or corresponding lactates, for example polya ida 4, polia ida 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides 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 terephthala ida or poly-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example 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, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and diolee and / or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as copolyether block esters derived from polyethers terminated in hydroxyl; and also poly-esters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyether sulfones and polyether ketones. 21. Interlaced polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as phenol / formaldehyde resins, urea / for aldehyde resins and melaimine / formaldehyde resins. 22. Alkyd resins drying and not drying. 23. Unsaturated polyester resins, derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and also their halogen-containing modifications of low flammability. 24. Interlazable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates. 25. Alkyd resins, polyester resins and acrylate resins entangled with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 26. Interlaced epoxy resins, derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of diglycidyl ethers of bisphenol A and bisphenol F, which are entangled 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 cellulose ethers such as methyl cellulose; as well as turpentine resins and their derivatives. 28. Mixtures of the aforementioned polymers (polyblends), for example PP / EPDM, Polia ida / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, 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. Organic materials of natural and synthetic origin that are pure onomeric compounds or mixtures of these compounds, for example mineral oils, fats, animals and vegetables, oils and waxes, or oils, fats and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitrates) and also mixtures of synthetic esters with mineral oils in any proportions by weight, typically those used as centrifugation compositions as well as aqueous emulsions of these materials. 30. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latexes of carboxylated styrene / butadiene copolymers. The invention further relates to a composition comprising an organic material subject to thermal or light-induced oxidative degradation and a stabilizing mixture according to the present invention. The organic material to be stabilized is preferably a synthetic polymer, more particularly one selected from the aforementioned groups. Polyolefins and polyethylene and polypropylene are particularly preferred. A preferred organic material is also a thermoplastic polymer or a binder for coatings.

The amount of stabilizer mixture to be used depends on the organic material that is stabilized and the intended use of the stabilized material. In general, it is appropriate to use for example 0.01 to 10% by weight of the total amount of stabilizer mixture, with respect to the weight of the material to be stabilized, preferably 0.01 to 5%, in particular 0.05 to 1%. The stabilizer mixture can be added, for example, to the polymeric materials, before, during or after polymerization or interlacing of the materials. In addition, the stabilizer mixture can be incorporated into the polymeric materials in pure form or encapsulated in waxes, oils or polymers. In general, the stabilizer mixture according to the invention can be incorporated into the organic materials to be stabilized by various processes, such as dry mixing in the powder form, or wet mixing in the form of solutions or suspensions or also in the form of a master batch; in these operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latexes. Also, the simple components of the stabilizer mixture according to the present invention can be added to the material to be stabilized.

The materials stabilized with the stabilizer mixture according to the present invention can be used for the production of molded parts, films, tapes, monofilaments, fibers, surface coatings and the like. If desired, other conventional additives for synthetic polymers, such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers, corrosion inhibitors and metal deactivators, may be added to the organic materials containing the stabilizer mixture in accordance with the present invention. Particular examples of conventional additives are: 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2, 6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-di-methylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-ethoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2, 6 di-nonyl-4-methylphenol, 2,4-dimethyl-6- (l -methylundec-l / -yl) phenol, 2,4-di-methyl-1-6- (1'-methylheptadec-1 '-yl) phenol , 2,4-dimethyl-6- (1'-methyltridec-1-yl) phenol and mixtures thereof. 1.2. Alkyltiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones f for example 2, 6-di-tert-butyl-4-methoxy-phenol, 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-d? -ter-but? l-4-hydroxanisole, 3, 5-d? -tert-butyl-4-hydroxyphenyl stearate, bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate. 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, β-tocopherol, 5-tocopherol and their mixtures (Vitamin E). 1.5. Hydroxylated thiodiphenyl ethers f 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) isulfide. 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'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidebisbis (4,6-di-tert-butylphenol), 2,2'-ethylidebis (6-tert-butyl-4-isobutylphenol), 2 , 2'-methylenebis [6- (a-methylbenzyl) -4-nonyl phenol], 2,2 '-methylenebis [6- (, -dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-ter) -butyl-2-methylfol), 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) -Utane, 1,1-bis (5-tert-butyl-4-hydroxy-2) -methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5) -methyl-f-enyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3, 5-dimethyl-2-hydroxy-enyl) -butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxy phenyl) -panolene, 2,2-bis- (5-tert-butyl) 4-hydroxy-2-methyl-phenyl) -4-n-dodecyl mercaptobutane, 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-dime-ilbenzylmercaptoacetate, 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-hydroxy-benzyl) 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. Hydroxybenzyl aromatic compounds, for example 1,3,5-tr is- (3,5-di-tert-butyl-4-hydroxy-benzyl) -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-bu ti 1 -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-hydroxy-enoxy) - 1, 3, 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-enoxy) -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-dimethyl-benzyl) -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-hydroxy-enylpropionyl) - 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, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester. 1.12. Acyl inophenols, for example 4-hydroxylauranylide, 4-hydroxysteatenylidene, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. 1.13. Esters of ñ- (3 f 5-di-tert-butyl-4-hydroxyphenyl-propionic acid, with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexandiol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri eti l in gl i co l, penta eri tri to l, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexan-diol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6,7-trioxabicyclo [2.2.2] octane. fí-f5-tert-butyl-4-hydroxy-3-ethylphenyl) propionic acid, with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane -diol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri eti l en gl i co l, penta eri tri to l, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thiaundecanol, 3-thiapentadecanol, tri ethylhexandiol, trimethylolpropane, 4-idroxymethyl-1-phosph a-2, 6,7-trioxabicyclo [2.2.2] octane. 1.15. Esters of β- (3,5-dichlohexyl-4-hydroxyphenyl-1-propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) -isocyanurate, N, N'-bis (idroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-l-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 poly alcohols -ldrich, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phe-2,6,7-tri oxabicyclo [2.2.2] octane. 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bie (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine. 1. 18. Ascorbic acid (vitamin C) 1.19. Antioxidants aminicoe, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylene-diamine, N, N'-bis (1,4-dimethylphenyl) - pf enylene diamine, N, N'-bis (l-ethyl-3-methylpentyl) -pf enylene diamine, N, N'-bis (l-methylheptyl) -pf enylene diamine, N, N'-dicyclohexyl- p-Phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N '-f-enyl-p-phenylene diamine, N- (1 , 3-dimethylbutyl) -N'-f-enyl-p-enylenediamine, N- (l-methylheptyl) -N'-phenyl-p-enylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p. -tolueneulfamyl) di-f-enylamine, N, N'-dimethyl-N, N'-di-eec-butyl-p-phenylene-diamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-dif-enylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -l-naphthylane, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di -tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoyl-a enol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino-methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl-methane, N, N , N ', N'-tetramethyl-4,4'-diaminophenylmethane, 1,2-bie [(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 di-alkylated tert-butyl / tert-octyldiphenylamines, a mixture of monocyclic nonylphenylamines or di-alkylated, a mixture of mono- and di-alkylated dodecyldiphenylamines, a mixture of mono- and di-alkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and di-alkylated tert-butyldiphenylanes, 2,3-dihydro-3 , 3-dimethyl-4H-l, 4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated ter-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N , N ', N'-tetraphenyl-l, 4-diaminobut-2-ene, N, N-bis- (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylene) diamine, bis (2, 2, 6, 6, -tetramethylpiperid-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperid-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. 2. UV Absorbents and Light Stabilizers 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'-hydroxy-enyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1, 1, 3,3-tetra ethylbutyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2' -hydroxy-enyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- methyl-f-enyl) -5-chloro-benzotriazole, 2- (3 '-sec-butyl-5'-tert-butyl-2'-hydroxy-enyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylheyl-yl) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5 -chloro-benotriazole, 2- (3 '-ter-but il-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'-hydroxy-enyl) -benzotriazole, 2- (3' -dodecyl-2'-hydroxy-5'-methylphenyl) - benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyl-oxycarbonylethyl) f-enylbenzotriazole, 2,2'-methylene-bis [1,1,3,3-tetramethylbutyl] - 6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl. 2.2. 2-Hydroxybenzophenonesf for example the derivatives 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy. 2.3. Esters of substituted and unsubstituted benzoic acids, such as for example 4-tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bie (4-tert-butylbenzoyl) reeorcinol, 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-hydroxy-benzoate, 2-methyl-4 , 6-di-tert-butyl-phenyl 3,5-di-tert-butyl-4-hydroxybenzoate. 2. 4. Acrylates, for example ethyl a-cyano-β, β-diphenylacrylate, isooctyl a-cyano-β, β-di-phenylacrylate, methyl-carbometoxycinnamate, methyl a-cyano-β-methyl-p-methoxy-cinnamate, butyl -cyano-ß-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline. 2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis- [4- (1, 1, 3,3-tetra-methylbutyl) phenol], such as the 1: 1 or 2: 1 complex, with or without additional ligands such as n-butylamine, triethanolamine, or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of the mono-alkyl esters, for example methyl or ethyl ester of 4-hydroxy-3,5-di -tert-butylbenzylphosphonic acid, nickel ketoximes complexes, for example 2-hydroxy-4-methylphenyl undecylcexime, methylphenyl undecylketoxime nickel complexes, l-phenyl-4-lauroyl-5-hydroxypyrazole nickel complexes with or are additional ligands. 2.6. Sterically hindered amines, for example bis (1, 2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of l- (2- hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N, N '-bi s (2, 2, 6, 6 - 1 etr amethyl 1-4 -piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, trie (2, 2, 6,6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis (2,2,6,6- tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethyl-piperazinone), 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-butyl-benzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decan-2, 4- dione, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethylpiperidyl) succinate, the condensation product N, N'-bis (2, 2, 6, 6-tetramet and 1-4-piperidyl) hexamethylene diamine and 4-morpholin-2,6-dichloro-l, 3,5-triazine, the product of condensation of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -l, 3,5-triazine and 1,2-bis (3-aminopropyl-amino) ethane , the condensation product of 2-chloro-4,6-di- (4-n-butylamino-1, 2,2,6,6-pentamethyl-piperidyl) -1,3,5-triazine and 1, 2 -bis- (3-aminopropylamino) -ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-l, 3,8-triazaspiro [4.5] decan-2,4-dione, 3-dodecyl -l- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-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-stearyloxy-2,2,6,6-tetramethylpiperidine, a product of N, N'-bis (2, 2, 6, 6-tetr. amet i 1-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis (3-amino-propylamino) ethane and 2,4 , 6-trichloro-l, 3,5-triazine as well as 4-but ilamino-2,2,6,6-tetra-methylpiperidine (CAS Registry No. [136504-96-6]); N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl- 7, 7,9, 9-tetramethyl-l-oxa-3,8-diaza-4-oxo-eepiro- [4,5] decane, a reaction product of 7,7,9,9-tetramethyl-2- cycloundecyl-l-oxa-3, 8-diaza-4-oxospiro- [4,5] decane and epichlorohydrin. 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxyanilide, 2,2'-didodecyloxy-5,5'-di- ter-butoxyanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and its mixture with 2-ethoxy-2 ' -ethyl-5,4'-di-tert-butoxyanilide and mixtures of ortho- and para-methoxy disubstituted oxanilides and mixtures of p-ethoxy disubstituted oxanilides. 2.8. 2- (2-Hydroxyphenyl-1,3,5-triazinesf 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-octyloxy-phenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -l, 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-butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -l, 3,5-triazine, 2- [2-hydroxy-4] - (2-hydroxy-3-octyloxy-propyloxy) -phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) ) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -l, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-di-methylphenyl) -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- hydroxy-propoxy) phenyl] -l, 3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxy) xyphenyl) -6-phenyl-1, 3,5-triazine. 3. Metal deareators, for example N, N-diphenyloxamide, N-sa 1 ici 1 to 1 -N '- sa 1 ici 1 oi 1 hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,4,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (ealicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide. 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphitoe, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-ter) -butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) entaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite , 6-isooctyloxy-2, 4,8, 10-tetra-tert-butyl-12H-di-benz [d, g] -l, 3,2-dioxaphosphocin, 6-fluoro-2,4,8,10- tetra-tert-butyl-12-methyl-dibenz [d, g] -1, 3, 2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2, 4-di) -tert-butyl-6-methylphenyl) ethylphosphite 5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamin a, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexa eci1-N-octadecyl-hydroxylamine, N-heptadecyl-N- Octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones, for example N-benzyl-alpha-phenyl-nitrona, N-ethyl-alpha-methyl-nitrona, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl- alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl- alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N, N-dialkyl-hydroxyaline derived from hydrogenated tallow amine. 7. Thiosineratists, for example dilauryl thiodipropionate or distearyl thiodipropionate. 8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl sterers, mercapto-benzimidazoles or the zinc salt of dibutylthiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese. 10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example stearate calcium, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and palmitate from < sodium, pyrocatecholium of antimony or tin pyrocatechollate. 11. Nucleating agents, for example inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metal; organic compounds such as mono- or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers"). 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, sawdust and powders or fibers of other natural products, synthetic fibers. 13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agent. 14. Benzofuranones and indolinones, for example those described in U.S. Patents. US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, 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-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3 - [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bie [5, 7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) -benzofuran-2 -one], 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzo-furan-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-ter -butyl-benzofuran-2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-1-benzofuran-2-one. The weight ratio of the stabilizer mixture according to the present invention to conventional additives can be, for example, 1: 0.5 to 1: 5.

Of particular interest is the use of the stabilizer mixture according to the invention as a stabilizer for coating, for example for paints. The invention therefore also relates to compositions wherein the material to be stabilized is a film-forming binder for revegetation. The novel coating composition preferably comprises 0.01-10 parts by weight of the stabilizer mixture according to the invention, in particular COS 10 parts by weight, especially 0.1-5 parts by weight per 100 parts by weight of the binder (in solid form) . Multilayer systems are also possible here, where the concentration of the stabilizing rocking according to the invention in the outer layer can be higher, for example from 1 to 15 parts by weight, especially 3 to 10 parts by weight per 100 parts. by weight of the binder (in solid form). The use of the stabilizer mixture according to the invention as a stabilizer in coatings has the additional advantage that release, ie separation of the substrate coating, is avoided. This advantage is particularly important in the case of metal substrates, including in the case of multilayer systems in metal substrates.

The binder (material to stabilize) can in principle be any binder that is usual in the industry, for example those described in the Encyclopedia of Chemical Industry of Ullmann (Ullmann's Encyclopedia of Industrial Chemistry), 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim, 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly based on a thermosetting resin. Their examples are alkyd, acrylic, polyether, phenolic, melamine, epoxy and polyurethane resins and their mixtures. The material to be stabilized can be a cold-curable or hot-curable binder; It can be advantageous to add a cure catalyst. Suitable catalysts that accelerate the curing of the binder are described for example in the Ullmann Encyclopedia of Chemical Industry (Ullmann's Encyclopedia Industrial Chemistry), Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim, 1991. Preference is given to coating compositions wherein the material to be stabilized is a binder comprising a functional acrylate resin and an entanglement agent. Examples of coating compositions containing specific binders are: 1. Paints based on cold or heat-curable alkyd, acrylate, polyester, epoxy or melamine or mixtures of these resins, if desired, with the addition of a cure catalyst; 2. Two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins, and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 3. One-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates, which are unblocked during baking; 4. Paintings of doe componen with baee (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 5. Two-component paints based on (poly) ketimines and an unsaturated acrylate resin, or a polyacetoacetate resin or a methacrylamidoglycolate methyl ether; 6. Two-component paints based on polyacrylates containing carboxyl or amino and polyepoxides; 7. Two-component paints based on acrylate resins containing anhydride and a polyhydroxyl or polya ino component; 8. Paints of two components based on anhydrides and polyepoxides containing acrylate; 9. Two-component paints based on (poly) oxazolines and acrylate resins containing anhydride or acrylate-unsaturated resins or isocyanates, isocyanurates or aliphatic or aromatic polyisocyanates; 10. Two-component paints based on polyacrylates and unsaturated polymalonate; 11. Thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally interlaced acrylate resins, in combination with etherified melamine resin and melamine; 12. Paint systems based on acrylate resins modified with fluoride or modified with siloxane. In addition to the material to be stabilized and the stabilizer mixture according to the invention, the novel coating composition may comprise, as an additional component, an additional light stabilizer of the sterically hindered amine type and / or 2-hydroxyphenyl-2H-benzotriazole and / or a 2- (2-hydroxyphenyl) -l, 3,5-triazine, for example as mentioned in the previous list under points 2.1, 2.6 and 2.8. The efficiency of the stabilizer mixture according to the invention can be particularly improved, when the additional component, a UV absorber based on hydroxyphenylbenzotriazoles and / or hydroxybenzophenones and / or oxyalic anides and / or hydroxyphenyl-s-triazines, for example as previously mentioned the previous list, under points 2.1, 2.2, 2.7 and 2.8, are present.

The additional component is preferably used in the amount of 0.05 to 5 parts by weight per 100 parts by weight of the binder (in solid form). In addition to the material to be stabilized and the stabilizer mixture according to the invention, the coating compositions may comprise additional components, for example solvents, pigments, colorants, plasticizers, stabilizers, thixotropic agents, drying catalysts and / or flow control agents. . Examples of possible components are those described in Ullmann'e Encyclopedia of Induetrial Chemistry, (Encyclopedia of Chemical Industry of Ullmann) 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim, 1991. Possible drying catalysts or curing agents are, for example, organometallic compounds, amines, resins containing amino and / or phosphine. Examples of organometallic compounds are metal carboxylates, in particular those of the metals Pb, Mn, Co, Zn, Zr and Cu, or metal chelates, in particular those of the metals Al, Ti and Zr, or compound and organoalicae, for example organotin compounds. Examples of metal carboxylates are the stearates of Pb, Mn and Zn, the octanoates of Co, Zn and Cu, the naphthenates of Mn and Co and the corresponding linoleates, reeinates and talates.

Examples of metal chelates are the aluminum, titanium and zirconium chelates of acetylacetone, ethyl acetylacetate, salicylic aldehyde, salicylate aldoxime, o-hydroxyacetophenone and ethyl trifluoroacetylacetate, and the alkoxides of these metals. Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate and dibutyltin dioctanoate. Examples of amines in particular are tertiary amines, for example tributylamine, triethanolane, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine and diazabicyclooctane (triethylenediamine) and their salts. Additional examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride. Resins that contain amino, are simultaneously binder and curing catalyst. Their examples are amino-containing acrylate copolymers. The cure catalyst can also be a phosphine, for example triphenylphosphine. The novel coating compositions can also be radiation curable. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds that are cured, after application by actinic radiation, that is to say they are converted into a high interlaced molecular weight form. UV curing system, also generally contain a photoinitiator. Corresponding systems are described in the aforementioned Ullmann's Encyclopaedia of Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453. In radiation curable coating compositions, novel stabilizing mixtures can also be used without the addition of sterically hindered amines. The novel coating compositions can be applied to any desired substrates, for example to metal, wood, plastic or ceramic materials. They are preferably used as top coatings in automotive paint. If the upper coating comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used either for the upper layer or for both layers, but preferably for the upper layer. The novel coating compositions can be applied to the substrates by conventional processes, for example by brushing, spraying, pouring, immersion or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, p. 491-500. The curing of the coatings can - depending on the binder system - be carried out at room temperature or by heating. The coatings are preferably cured at 50-150 ° C, powder coatings also at higher temperatures. The coatings obtained according to the invention have excellent resistance to the harmful effects of light, oxygen and heat; Particular mention should be made of the good light and coating resistance of the coatings, for example paints, obtained in this way. The invention therefore also relates to a coating, in particular a paint, which has been stabilized against the ill effects of light, oxygen and heat, by a content of the stabilizing rocking according to the invention. The preferred paint is a final coating or coating for automobiles. The coating compositions may comprise an organic solvent or solvent solvent in which the binder is soluble. However, the coating composition can also be an aqueous solution or dispersion. The vehicle can also be a mixture of an organic solvent and water. The coating composition can also be a high solids paint or does not contain a solvent (powder paint).

The pigments can be inorganic, organic or metallic pigments. The novel coating compositions preferably do not contain pigments and are used as clear coatings. Also preferred is the use of the coating composition as a final coating for applications in the automotive industry, in particular as a final pigmented or non-pigmented finish coating. However, the use for underlying layers is also possible. The compounds of the formula (I) can also be used as stabilizers, especially as light stabilizers, for almost all materials known in the art of photographic reproduction and other reproduction techniques, for example as described in Research Disclosure 1990 (Description of Research, 1990), 31429 (pages 474 to 480). The examples below dictate the invention in greater detail. In the examples, parts and percentages are given by weight; the ambient temperature is taken which means a temperature in the range of 20 to 25 ° C. These definitions apply unless otherwise stated in each case. Examples of stabilizer mixtures according to the invention are illustrated in Table 1 below.

Table 1: Mixture R n Analysis P. fusion No. [% (chromate gas ene graph)] 101 H 2 (25), 3 (39), 4 (27) c% 67.28 66.41 65-109 H% 10.31 10.12 N% 6.82 6.52 102 Me 2 (26), 3 (40), 4 (24) c% 68.45 68.14 - H% 10.57 11.33 N% 6.39 6.39 103 H 2 (20), 3 (52), 4 (15) C% 67.28 65.62 47- 74 H% 10.31 10.51 N% 6.82 6.37 104 Me 2 (21), 3 (55), 4 (15) C% 68.45 66.55 H% 10.57 10.86 N% 6.39 6.86 105 H 3 (79), 4 (20) C% 66.95 67.1 67.77 H% 10.75 10.93 N% 6.79 6.61 106 Me 3 (74), 4 (23) C% 68.14 66.82 Table 1 f Continuation1: Mixture R n Analysis P. fusion No. [% (chromate gas ene. Gas graph 11 H% 10., 98 11.0 N% 6., 36 6.13 107 H 3 (9), 4 (85) C% 68. .21 66.58 78 -87 H% 10., 02 10.74 N% 6. .63 6.10 108 Me 3 (9), 4 (82) C% 68., 18 68.02 78-87 H% 10., 10 10.92 N% 6., 24 5.85 109 H 7 (47), 8 (48) C% 69. .73 69.48 H% 10., 85 10.80 N% 5, .91 5.26 110 H 4 (42), 7 (49) C% 68. .72 68.63 75-80 H% 10, .63 10.91 N% 6. .29 6.07 111 Me 4 (43), 7 (42) C% 69, .73 68.92 H% 10, .85 10.84 N% 5, .91 5.85 112 H / Me 8 (100) C% 70, .40 70.20 (1: 1) H% 11, .00 11.43 N% 5, .66 5.63 113 H / Me 2 (20, 3 (40), 4 (20 ) C% 67, .89 67.16 Table 1 (Continued): Mixture R n Analysis P. fusion No. [% (chromate gas ene graph)], H% 10.44 10.55 N% 6.60 6.51 114 Me 3 (70.3), 4 (22.4) C% 68.14 68.10 H% 10.98 10.84 N% 6.36 6.29 115 -O- 2 (20), 3 (52), 4 (15) 41-42 116 OC.H ,, 2 (20 ^ f3 (52 f4 (15) - Example 1; Preparation of mixture No. 101. a) 19.6 g (0.2 mol) of concentrated sulfuric acid are added dropwise to a solution of 26.4 g (0.2 mol) "mixture of dicarboxylic acid 11 ex" "BASF in 200 ml of methanol at room temperature The reaction mixture is refluxed for 3 hours.The column is neutralized with 27.6 g (0.2 mol) of potassium carbonate. , empty in a saturated NH4C1 solution and extract with ethyl acetate.The organic extracts are dried (brine, Na2SO4) and concentrated in vacuo to give 32 g (100%) of the desired methyl ester mixture as a colorless liquid. GC (gas chromatography) / MS (mass spectrum) MW (molecular weight) 115 g / mol (28.3%), MW 129 g / mol (42.5%), MW 143 g / mol (29.2%). b) A mixture of 26.7 g (0.15 mol) of the methyl diesters described in example la), 58 g (0.38 mol) of 2,2,6,6-tetramethylpiperidin-4-ol and 1.5 g (6 mmoles) of dibutyl tin oxide is heated to 150 ° C while methanol is removed by distillation. After 2 hours, a slight vacuum (300 mbar) is applied to the reaction mixture and stirring is continued for another 10 hours at 150 ° C. The reaction mixture is cooled, diluted with hexane, filtered and concentrated in vacuo. The excess piperidinol is removed by distillation (bead tube: 170 ° C / 0.08 mbar) to give the title mixture as an amorphous white solid (melting range: 40-65 ° C). Example 2: Preparation of mixture No. 102. This mixture is prepared according to the procedure of Example 1, using 16 g (0.1 mol) of the diester mixture described in Example la), 42.8 g (0.25 mol) of 1, 2,2,6,6-pentamethylpiperidin-4-ol and 1 g (4 mmoles) of oxide of dibutyltin 34 g (78%) of the mixture No. 102 are obtained as a viscous oil. Example 3: Preparation of mixture No. 103. This mixture is prepared according to the procedure of Example 1, using 8 g (0.05 mol) of "^ DBE (commercially available mixture of succinic, glutaric and adipic acid methyl esters in the ratio of 20:59:21 ex MRDu Pont), 20.44 g (0.13 mmol) of 2, 2, 6, 6-tetramethylpiperidin-4-ol and 0.62 g (2.5 mmol) of dibutyltin oxide 16.5 g (81% ) of mixture No. 103 are obtained as an amorphous solid (melting range: 45-74 ° C) Example 4: Preparation of mixture No. 104 This mixture is prepared according to the procedure of Example 1, using g (0.05 mol) of "" DBE (commercially available mixture of methyl esters of succinic, glutaric and adipic acids, in the ratio of 20:59:21 ex MEDu Pont), 19.7 g (0.115 mmol) of 1.2.2 , 6,6-pentamethylpiperidin-4-ol and 0.62 g (2.5 mmoles) of dibutyltin oxide 19.3 g (88%) of the mixture No. 104 are obtained as a viscous oil. Ezcla No. 105 A soldeneion of 11.4 g (0.07 mol) of MRDBE2 (commercially available mixture of methyl esters of glutaric and adipic acid in the proportion of 77:23 ex "" Du Pont) and 26.4 g (0.17 mol) of 2, 2,6,6-tetramethylpiperidin-4-ol in 30 ml of xylene, heated to 80 ° C. Lithium amide (0.08 g, 3.5 mmol) is added to the resulting solution and the mixture is heated to 145 ° C resulting in the distillation of methanol. The mixture is stirred for an additional 15 hours. After cooling to 80 ° C, acetic acid (0.3 g, 5 mmol) is added and the reaction mixture is diluted with hot toluene, filtered and concentrated in vacuo. After distillation of the excess piperidinol (bead tube: 180 ° C / 0.1 mbar), 20 g (69%) of the mixture No. 105 are obtained as a white solid (melting range: 67-77 ° C).

Example 6: Preparation of mixture No. 106. A mixture of 11.4 g (0.07 mol) of MRDBE2 ex HRDu Pont (see Example 5) and 26.4 g (0.15 mol) of 1,2,2,6,6-pentamethylpiperidin- 4-ol is dried by adding 10 ml of toluene and then heating under vacuum (200 mbar) at 140 ° C to remove the water-toluene azeotrope. The vessel is pressurized with nitrogen and 0.7 g (3.5 mmoles) of aluminum isopropoxide are added. The reaction mixture is heated to 160 ° C resulting in the distillation of methanol. After 1 hour, vacuum is applied per (300 mbar), and the mixture is stirred for an additional 15 hours. After cooling to approximately 80 * 0, acetic acid (0.3 g, 5 mmol) is added and the reaction mixture is diluted with toluene, filtered and concentrated in vacuo. After distillation of the excess piperidinol (bead tube: 180 ° C / 0.1 mbar), 26.3 g (85%) of the No. 106 mixture are obtained as an oil. Example 7: Preparation of mixture No. 107. This mixture is prepared according to the procedure of Example 1, using 12.1 g (0.07 mol) of "" DBES (commercially available mixture of methyl esters of glutaric and adipic acid in the proportion from 10:90 ex "" Du Pont), 23.6 g (0.15 mol) of 2, 2, 6, 6-tetramethyl-piperidin-4-ol and 0.7 g of (2.8 mmol) of dibutyltin oxide. 20 g (68%) of the mixture No. 107 are obtained as an amorphous solid (melting range: 78-87 ° C).

Example 8: Preparation of mixture No. 108. This mixture is prepared according to the procedure of Example 1, using 12.1 g (0.07 mol) of MRDBE3 (commercially available mixture of methyl esters of glutaric and adipic acid in the proportion of 10%). : 90 ex "" Du Pont), 26.4 g (0.15 mol) of 1, 2, 2,6,6-pentamethyl-piperidin-4-ol and 0.7 g of (2.8 mmol) of dibutyltin oxide. 28 g (89%) of the mixture No. 108 are obtained as an amorphous solid (melting range: 78-87 ° C). Example 9: Preparation of mixture No. 109. A suspension of 6.5 g (0.041 mol) of 2,2,6,6-tetramethylpiperidin-4-ol and 4.9 g (0.048 mol) of triethylamine in 150 ml of 1.2 - Dichloroethane is cooled to about 5 ° C. A mixture of 2.25 g (0.01 mol) of azelaic acid dichloride and 2.39 g (0.01 mol) of sebacoyl chloride is added dropwise and the cooling bath is removed. The thick white suspension obtained is heated to 60 ° C. for 5 hours.After cooling to room temperature, the reaction mixture is filtered and concentrated in vacuo.The residue is dried under high vacuum (70 ° C / 0.08 mbar) to give 9.32 g (98%) of mixture No. 109 as a pale orange oil Example 10: Preparation of mixture No. 110. This mixture is prepared according to the procedure of Example 5, using 22.65 g (0.144 mol) of 2,2,6,6-tetramethylpyperidin-4-ol, 5.23 g (0.03 mol) of methyl adipate, 6.49 g (0.03 mol) of methyl azelate and 0.07 g (3 mmol) of lithium amide, 20.5 g of (77 %) of the mixture No. 110 are obtained as a white solid (melting range: 75-80 ° C) Example 11: Preparation of the mixture No. 111 This mixture is prepared according to the procedure of Example 1, using 25.65 g (0.15 mol) of l, 2,2,6,6-pentamethylpiperidin-4-ol, 5.23 g (0.03 mol) of methyl adipate, 6.49 g (0.03 mol) of methyl azelate and 0.75 g (3 mmol) of dibutyltin oxide 25.9 g (91%) of the mixture No. 111 are obtained as an orange oil. Example 12: Preparation of mixture No. 112. This mixture is prepared according to the procedure of Example 1, using 10.22 g (0.065 mol) of 2,2,6,6-tetramethylpiperidin-4-ol, 11.13 g (0.065) mol) of 1, 2,2,6,6-pentamethylpiperidin-4-ol, 11.52 g (0.05 mol) of methyl sebacate and 58 mg of | MRFascat 9201"(polymer-tinned catalyst of"? lf Atochem). 24.5 g (98%) of the mixture No. 112 are obtained as a brown oil. Example 13: Preparation of mixture No. 113. This mixture is prepared according to the procedure of Example 1, using 15.7 g (0.1 mol) of 2,2,6,6-tetramethylpiperidin-4-ol, 5.14 g (0.03). mol) of 1, 2,2,6,6-pentamethylpiperidin-4-ol, 8 g (0.05 mol) of MBDBE of • "Du Pont (see Example 3) and 58 mg of l | MRFascat 9201" (catalyst based on polymeric tin of ^ Elf Atochem). 14 g (70%) of the mixture No. 113 are obtained as a brown oil. Example 14: Preparation of mixture No. 114. 12 g (0.07 mol) of 1, 2, 2, 6, 6-pentamethylpiperidin-4-ol are dried by heating under vacuum (100 mbar) at 140 ° C for 1 hour 30 minutes (water separation). After cooling to 100 ° C, the vessel is pressurized with nitrogen and 5.7 g (0.035 mol) of MRDBE2 (MRDu Pont; see Example 5) followed by 0.45 ml (1.75 mmoles) of aluminum sec-butylate is added. The reaction mixture is heated to 165 ° C resulting in the distillation of methanol. After 30 minutes a vacuum is applied (200 mbar) and the mixture is stirred for an additional 5 hours. After cooling to about 80 ° C formic acid (0.2 ml) is added, the reaction mixture is diluted with toluene, poured into water and extracted with toluene. The organic extracts are dried (brine, Na2SO4) and concentrated in vacuo to give 14.6 g of a pale yellow oil. The unreacted piperidinol is removed (150 ° C / 0.1 mbar / 2 hour pellet tube) to give 13.5 g (88%) of the titrant No. 114 as a light yellow oil. Example 15: Preparation of mixture No. 115. Traneetherification of 49.8 g of the "" DBE (0.3116 mol) (MRDu Pont; see Example 3) with 111.6 g of nitroxyl 2,2,6,6-tetramethyl-4-hydroxypiperidine (0.6294 mol) and TPT catalysts (3.22 g, 0.011 mol) [TPT = tetraisopropyl titanate] in 350 g of n-heptane is completed in 7 hours, with the vessel temperature being maintained at 97-99 ° C while the The upper temperature was in the range of 64-96"C during removal of MeOH.The batch is diluted with 30 g of n-heptane and the TPT catalyst treated with 20 g of deionized water at 90 ° C, and then azeotroped to 100 ° C and filtered The product solution is washed with 5 x 100 g MeOH: H20 (10%) at 70 ° C to remove excess nitroxyl 2,2,6,6-tetramethyl-4-hydroxypiperidine, and then azeotropically dried at 100 ° C. The batch was slowly cooled to the crystallization point 41-42 ° C, and further cooled to 10 ° C. The batch was filtered and rinsed with cold n-heptane and then dried. to give a red solid, 124.3 g (90.7% isolated yield). Example 16: Preparation of mixture No. 116. Conversion of MRDBE dinitroxyl (No. 115, Example 15) to the re-active NO-octyl derivative is effected by reacting 51 g of dinitroxyl (0.1159 mol), 0.13 g of Mo03 (0.0009 mol) , 228 g of n-octane (1,996 moles) with 36.5 gx 70% t-butylhydroperoxide (0.4050 mol) which is added over 1.75 hours at 95-110 ° C. The reaction temperature is allowed to increase to 118 ° C by separation of distilled H20 / t-butanol / n-octane using a 5-stage Oldershaw column and maintained for a total of 13 hours. The reaction mass is cooled to 55 ° C and Mo03 is removed by filtration. Insulation required 27.8 g of 11% sodium sulfite treatment in combination with 2.5 g of 20% NaOH at 55 ° C for 1 hour. The aqueous layer was then removed and the organic layer was neutralized by the addition of 20 g of deionized H20 and acetic acid. "" Darco KB44 (5 g) (m of ICI, activated carbon) is then loaded and the solution is heated to 70 ° C and maintained for 1 hour. After filtration and detachment at 70 ° C under high vacuum, a light yellow oil with% transmission of 425 nm, 450 nm and 500 nm is obtained which is 98.3%, 98.7% and 99.3%, respectively. Example 17: Stabilization of a 2-layer metallic finish. The light stabilizers to be tested are dissolved in g of Solveeso "" 100 and test in a transparent coating having the following composition: Synthacryl ™ SC 303x 27.51 g Synthacryl ™ SC 3702 23.34 g Maprenal ™ 6503 27.29 g Butyl Acetate / Butanol (37/8) 4.33 g Isobutanol 4.87 g Solvesso "1 * 1504 2.72 g Crystal Oil K-305 8.74 g Leveling aid BaysilonMR6 1.20 g 100.00 g 1 Acrylate resin, "" Hoechet AG, 65% solution in xylene / -butanol (26: 9) 2 Acrylate resin, "" Hoechst AG; 75% solution in Solvesso ™ 100"3 Melamine resin, MEHoechst AG; 55% solution in isobutanol Mixture of aromatic hydrocarbons, boiling range: 182-203 ° C (Solvesso *** 150) or 161 - 178 ° C (Solvesso ™ 100); maker; ^ Eseo 5 Mixture of aliphatic hydrocarbons, boiling range: 145 - 200 ° C; manufacturer: HBShell 6 1% in SolveseoMP 150; manufacturer: MBBayer AG 1% of the light stabilizer to be tested is added to the transparent coating, based on the solids content of the varnish. Some additional samples of varnish are prepared, which in addition to the novel compounds, contain 1. 5% of the compound of the formula: By comparison, a transparent coating that does not contain light stabilizer is used. The clearcoat is diluted with SolveseoMR 100 at a dew point and applied by spraying to a prepared aluminum panel ("" Uniprime Epoxy, silver metallic basecoat) which is baked at 130 ° C for 30 minutes to give a speci dry film of 40 -50 μm transparent coating.

The mueetrae are then exposed to the weather in an Atlas MRUVCON outdoor exposure unit (UVB-313 lamps) in a cycle comprising UV irradiation at 70 ° C for 8 hours and condensation at 50 ° C for 4 hours. The surface gloss (20 ° brightness as defined in DIN 67530) of the samples is then measured at regular intervals. The results are illustrated in Tables 2a-2d. Table 2a: Brightness stabilizer * 20 ° as defined in DIN 67530 of Light after 0, 1600 and 2000 hours of exposure to weathering in MRUVC0N fUVB-3131 0 hour 1600 hours 2000 hours None 87 ** (A) 87 28 13 ( B) 86 24 *** (C) 86 49 21 *: high values indicated a good stabilization **: shrinkage after 800 hours ***: shrinkage after 1600 hours Light stabilizers used: Light stabilizer (Al: R = -CH3; n = 4 Light stabilizer fB: R = -CH3; n = 7 Light stabilizers (O: Mixture No. 111 (R = -CH3; ratio of n = 4 (43 %) / 7 (42%)) Table 2b: Stabilizer Brightness * 20 ° as defined in DIN 67530 of Light after 0 and 1600 hours exposure to weathering in MRUVC0N (UVB-313 0 hour 1600 hours None 87 ** (D) 87 53 (E) 87 28 (F) 87 61 *: high Vllores indicated an huena **: shrinkage after 800 hours Light stabilizers used: Light stabilizers (D): R = -CH3; n = 3 Light stabilizers (El: R = -CH3; n = 4 Light stabilizers (F): Mixture No. 108 (R = -CH3; proportion of n = 3 (9%) / 4 (82%)) Table 2c: Brightness stabilizer * 20 ° as defined in DIN 67530 of Light after 0, 4000 and 4400 hours of weathering in "RUVC0N (UVB-313 ^ 0 hour 4000 hours 4400 hours None 87 ** MRTINUVIN 384 86 *** (A) + HRTINUVIN 384 87 85 41 (BJ + TINUVIN 384 87 75 25 (C) + MRTINUVIN 384 87 87 63 *: high values indicate a good stabilization **: cracking after 1200 hours ***: cracking after 2000 hours Light stabilizers used: MRTINUVIN 384 Light stabilizers (h): R = -CH3; n = 4 Light stabilizers (B): R = -CH3; n = 7 Light stabilizers (O: Mixture No. 111 (R = -CH3; proportion of n = 4 (43%) / 7 (42%)) Table 2d: Stabilizer Shine * 20 ° as defined in DIN 67530 Light after 0, 4000, 4400 and 4800 hours of exposure to the weather in MRUVCQN (UVB-3131 0 hour 4000 hrs 4400 hrs 4800 hrs None 87 ** MRTINUVIN 384 86 ** (G) + HRTINUVIN 384 87 75 25 ** ** (H) + MRTINUVIN 384 86 48 24 **** (I) + KRTINUVIN 384 87 88 64 33 high values indicate a good stabilization **: cracking after 1200 hours ***: cracking after 2000 hours ** **: fieuration after 4400 hours Light stabilizers used: TINUVIN 384 Light stabilizers (G): R = -CH3; n = 7 Light stabilization (Hl: R = -CH3; n = 8 Light stabilizers (I): Mixture No. 109 (R = -CH3; proportion of n = 7 (47%) / 8 (48%)) The results listed in Table 2a, 2b, 2c and 2d illustrate that they are stabilized with a stabilizing mixture, have a better weathering stabilizer (brightness retention) than the unstabilized sample or the sample stabilized with the simple components of the stabilizing mixture.

Example 18: Stabilization of polypropylene plates. 1 g of each of the compounds indicated in Table 3, 1 g of tris (2,4-di-tert-butylphenyl) -phosphite, 0.5 g of pentaerythritoltetraguis [3- (3,5-di-tert-butyl) 4-hydroxy-phenyl) propionate], 1 g of calcium stearate and 1 g of '"' Filofin Blue G (ex" "Ciba-Geigy), are mixed in a turbo mixer with 1000 g of polypropylene powder of index of fusion = 4 g / 10 minutes (measured at 230 ° C and 2.16 kg) The obtained mixtures are extruded at a temperature of 200-230 ° C to give polymer granules which are then added to plates with a thickness of 2 mm by molding by injection at 200-220 ° C. The plates obtained are exposed in Weather-O-Meter Model WE weather proofing device (ASTM D2565-85) with a black panel temperature of 63 ° C until surface embrittlement begins (powder disintegration) A polypropylene plate prepared under the conditions as indicated above but without the addition of the compounds of the invention, is disclosed comparison. In Table 3, the exposure time required to reach this onset of embrittlement is given in hours. The longer the time, the better the stabilizing effect.

Table 3: Light stabilizer Dust disintegration time (hours) None 570 (J) 4460 (K) 4050 () 5020 Light stabilizers used: Light stabilizer (J): R = H; n = 3 Light stabilizer (K): R = H; n = 4 Light stabilizer (L): Mixture No. 105 (R = H, ratio of n = 3 (79%) / 4 (20%)) The results listed in Table 3 illustrate that the sample stabilized with a mixture The stabilizer according to the invention had a better etchibility against powder disintegration than the non-stabilized sample or the samples stabilized with simple components of the stabilizing mixture.

Claims (18)

1. CLAIMS 1. A stabilizing mixture containing two different compounds of the formula (I) wherein n is an integer from 2 to 22 and R is hydrogen, alkyl having 1 to 8 carbon atoms, -O-, -OH, -NO, -CH2CN, alkoxy with 1 to 18 carbon atoms, cycloalkoxy with 5 to 12 carbon atoms, alkenyl with 3 to 6 carbon atoms, alkynyl with 3 to 6 carbon atoms, acyl with 1 to 8 carbon atoms or phenylalkyl with 7 to 9 carbon atoms unsubstituted or substituted in phenyl for 1, 2 or 3 alkyl having 1 to 4 carbon atoms; the weight ratio of the two compounds is 1:20 to 20: 1.
2. 2. Stabilizer mixture according to claim 1, characterized in that n is an integer of 2 to 10.
3. 3. Stabilizing mixture according to claim 1, characterized in that the two compounds of the formula (I) only differ in the variable n.
4. 4. Stabilizing mixture according to claim 1, characterized in that the two compounds of the formula (I) differ in the variable n and the difference between the two variables of n is 1, 2, 3, 4 or 5.
5. 5. Stabilizing mixture of compliance with claim 1, characterized in that the variable n of a compound of the formula (I) is 3 and the variable n of the other compound of the formula (I) is 4.
6. The stabilizer mixture according to claim 1, characterized in that the variable n of a compound of the formula (I) is 4 and the variable n of the other compound of the formula (I) is
7. 7. The stabilizer mixture according to claim 1, characterized in that the variable n of a composition of the formula (I) is 7 and the variable n of the other compound of the formula (I) ee
8. 8. The stabilizer mixture according to claim 1, characterized in that it additionally contains a third compound of the formula (I).
9. 9. Stabilizing mixture according to claim 1, characterized in that the variable n of a compound of the formula (I) is 2 and the variable n of the other compound of the formula (I) is 3; the mixture additionally contains a third compound of the formula (I) with n which is 4.
10. 10. Stabilizing mixture according to claim 1, characterized in that the two compounds of the formula (I) differ only the meaning of the group R.
11. 11. Stabilizing mixture according to claim 1, characterized in that R is hydrogen, alkyl with 1 to 4 carbon atoms, -OH, aleoxi with 1 to 8 carbon atoms, cycloalkoxy with 5 to 8 carbon atoms, allyl, benzyl, acetyl or acryloyl.
12. 12. The stabilizer mixture according to claim 1, characterized in that R is hydrogen or methyl.
13. 13. The stabilizer mixture according to claim 1, characterized in that it contains as an additional component a UV builder with bae in hydroxyphenylbenzotriazoles and / or hydroxybenzophenones and / or oxalic aniidas and / or hydroxyphenyl-s-triazines.
14. 14. A composition containing an organic material subject to degradation induced by thermal or oxidative light and a stabilizing mixture according to claim 1.
15. 15. A co-product according to claim 14, characterized in that the organic material is a synthetic polymer. .
16. 16. A composition according to claim 14, characterized in that the organic material is a thermoplastic polymer or a binder for coatings.
17. 17. A composition according to claim 14, characterized in that the organic material is a polyolefin.
18. 18. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, characterized in that it comprises incorporating a stabilizing mixture in the organic material according to claim 1.