MXPA98005329A - "n, n ', n"' tris (2,4-bis [(1-hydrocarbiloxy-2,2,6,6-tetrametilpiperidin-4-il) alkylamine] -s-triazin-6-il) -3, 3'-etilendiiminodipropilaminas, its isomers and derivatives with bridge link and polymeric compositions stabilized with the - Google Patents

Abstract

A mixture of the compounds identified in the title, their pure isomers and bridged derivatives with alkane are particularly effective in stabilizing stabilizing polymeric compositions, particularly polyolefin compositions.

Description

N, N ', N "' - tRlS { 2,4-BISr (1-HlDROCARBlLOXl-2,2,6,6-TETRAMET1LPIPERID1N-4-IÜALQUILAMIN01-S-TRIAZ1N-6-ILV3.3'- ET1LEND11M1NOD1PROP1LAM1NAS, ITS ISOMERS AND DERIVED WITH BRIDGE LINK AND POLYMERIC COMPOSITIONS STABILIZED WITH THEM The general invention relates to N, N ', N' "- tris. {2) 4-bis [(1-hydrocarbyloxy-2,216) 6 -tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamines, their pure isomers, and bridging derivatives and their stabilized polymer compositions. The present compounds, due to their low basicity, have a particular value for the stabilization of the polymeric compositions where the I | activity of the most basic amine stabilizers is significantly reduced due to the interaction with the polymeric substrate. Examples of the polyolefin compositions in which the present compounds are particularly effective include flame retardant polyolefins in which the acid residues from the decomposition of the halogenated flame retardants deactivate the normal hindered amine stabilizers, the films for greenhouses and many agricultural films in which the acid residues of pesticides interfere with the activity of normal hindered amine stabilizers, and thermoplastic polyolefins in which interactions with basic hindered amine stabilizers interfere with the paint of the substratum. BACKGROUND OF THE INVENTION The hindered N1N, N ", N '" - tetrakys substituted amines, which are described with the formula I where R1-R4 are all E, have been patented as less basic polymeric stabilizers, without interaction for various coatings for environmental and thermosetting automotive, polyolefin, and non-polyolefin applications as described in U.S. Patent No. 5,0,44.JJ0, 5,096,950; 5,204,473; 5,112,890 and 5,124,378; and in European Patent Application 309402 A1. Specifically, the preparation of N > N ', N ", N," - tetrak. { 2,4-b 's [(1-cyclohexylloxy-2I2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3'-etlendiminodipropylamine and its analogue I octyloxy was described by Winter et al., Respectively, in Examples 62 and 67 of US Pat. No. 5,204,473. The same patent also claims analogue 1-methoxy in Claim 25. None of the above patents contains any specific performance data on these hindered amine stabilizers of tetra-substituted s-triazine in any organic substrate. The present invention differs from the prior art in that the present compounds have an unsubstituted nitrogen on the main chain of the tetraamine I. Moreover, none of the prior art techniques, including US Pat. No. 5,015,682, which describes hindered N-hydrocarbon amine stabilizers, describes the bridging structures described by formulas II and III. Detailed description - invention présenle refers to a mixture of NlN, lN "'- lris { 2,4-bis [(1- idrocarbil-oxy¡-2I2l6,6-tetrametilp¡per¡din-4-il) alylamino] - s-tHazin-6-yl.} - 3i3, - ethylenediiminodipropylamine; N, N ', N "-tris. { 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3-ethylenediiminodipropylamine and its bridging derivatives as described in formulas I, II, HA and R? NH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4O) wherein in the tetraamine of the formula I, i and 2 are the porion E of s-triazine; and one of R3 and R4 is the E portion of s-triazine, the other being hydrogen R3 or R4, R is methyl, cyclohexyl or octyl, preferably cyclohexyloxy or octyl, R5 is alkyl of 1 to 12 carbon atoms, preferably n-butyl; where in the compound of the formula II or HA when R is cyclohexyl or octyl, T and Ti are each a tetraamine substituted by R1-R4 as defined in formula I, where (1) one of the E portions of s- triazine in each tetraamine is replaced by the group E1 which forms a bridge between the two tetraamines T and T1, or (2) the group E1 may have both terms in the same tetraamine T as in the formula IA where two of the E portions of tetraamine are replaced by an E1 group, or (3) all three s-triazine substituents of tetraamine T can be E1 so that E1 is linked to T and Ti and a second E1 has both terms on tetraamine T, i L is cyclohexanediyl or octanediyl; where, in the compound of the formula III G, Gi and G2 are each substituted by R, -R-? as defined in formula I, except that G and G2 have one of the S-triazine portions E replaced by Ei, and Gi has two of the triazine E-portions replaced by Ei, such that there is a bridge between G and Gi, and a second bridge between Gi and G2. The compounds of the formula I have two possible isomers bearing in mind that there is no bridge between the molecules. These two isomers are delineated in the following table. Isomer Ri R2 R3 R 1 EEHE 2 E 'EEH The mixture of the compound of the invention was prepared by reacting between two and four equivalents of 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-piperidin-4) -l) butylamino] -6-chloro-s-triazine with one equivalent of N, N'-bis (3-aminopropyl) ethylene diamine, especially by reacting 2-4 equivalents of 2,4-bis [(1-) hydrocarbyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) alkylamino] -6-chloro-s-triazine with 1 equivalent of N, N'-bis (3-aminopropyl) -ethylenediamine in a solvent of hydrocarbon with an acidic acceptor, such as, for example, aqueous sodium hydroxide, used to neutralize the hydrochloric acid produced in the reaction. The synthesis of several educts of the type 2,4-bis [(1-hydrocarbyloxy-2,6,6,6-tetramethylpiperidin-4-yl) alkyl-amino] -6-chloro-s-triazine is described in U.S. Patent Nos. 5,216,156 and 5,204,473. In a preferred process, between 2.5 to three equivalents of the s-triazine, especially three equivalents of s-triazine, are reacted with one equivalent of the amine.

The preferred method for the synthesis of 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -5-cyoro-s-triazines is to heat a mixture of 6-chloro -s-triazine substituted with amine hindered with tert-butyl hydroperoxide, a metal oxide catalyst and the suitable hydrocarbon solvent until the red color of the nitroxyl intermediate is discharged as explained in U.S. Patent No. 4,921,962. In some cases, two nitroxyl radicals will bond with the same solvent molecule. This is the source of the bridging material illustrated by formulas ll and III as we have described above. The N-methoxy compounds of the present invention do not contain these bridged structures because different synthetic methodology is used to generate hindered 1-methoxy substituted amines. U.S. Patent No. 5,204,473 describes the introduction of a 1-cyclohexyloxy or 1-1-octyloxy substituent on a hindered amine starting material of tetra-substituted s-triazine. The tris-substituted compounds present different from the tetra-substituted compounds of the prior art because they are prepared by means of a different route as illustrated below, even the use of 4 equivalents of the chloro-s-triazine intermediate, most of which of the product mixture is tris-substituted. The use of as little as 2 equivalents of the chloro-s-triazine intermediate even gives some tris-substituted product. The term "hydroxyloxy" here refers primarily to methoxy, cyclohexyloxy or octyloxy. In the compounds of the formula I-IU and therefore, in the products of the present process, R is usually cyclohexyl or octyl, and in the compounds of the formula I further includes the methyl. A mixture of compounds I-III is preferred, where R is cyclohexyl or octyl, especially a mixture of N, N ', N' "- tris, 2,4-bis [(1-cyclohexyloxy-2,2,6l6 -tetramethylpiperidin-4-yl) n-Dutylamino] -s-triazin-6-yl.} - 3,3'-ethylenediiminodipropylamine; N, N ', N "-tris. { 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazin-6-yl} -3,3'-ethylene-di-minodipropylamine and its bridging derivatives as described in formulas I, II, HA and III. Also of interest is a mixture of N, N ', N' "- tris., 2,4-bis [(1-octyloxy-) 2,2,6,6-tetramethyl-piperic-lin-4-yl. ) n-butylamino] -s-triazin-6-yl.} - 3,3'-ethylenediiminodipropylamine; N, N ', N "-tr¡s-. { 2,4-bis [(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazin-6-yl} -3,3'-ethylene-diiminodipropylamine especially n-butyl.

The compounds of the formulas I-III are especially well suited as stabilizers for the organic material against thermal, oxidative or light-induced degradation; They are also active as flame retardants.

Thus, the present invention also relates to a composition stabilized against thermal, oxidative or light-induced degradation comprising: I (a) an organic material prone to thermal, oxidative or light-induced degradation, and (b) an effective spraying amount of a compound of formula I, II, HA or III. Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, especially a thermoplastic polymer. More preferably, the polymer is a polyolefin, a thermoplastic olefin or polycarbonate. Of greater importance is a polyolefin, especially polyethylene or polypropylene. The compounds of this invention exhibit superior hydrolytic stability, superior handling and storage stability as well as good extraction resistance when present in a stabilized composition. The methodology for preparing the present compounds is described in the prior art. The intermediates needed to prepare the present compounds are widely commercial products.

In general, polymers that can be stabilized include 1. Polymers of monolefins and diolefins, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methyl-1-en-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example, of cyclopentene or norbornene, polyethylene (which may optionally be crosslinked), for example, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyethylene i of low density branched (BLDPE). The polyolefins, for example, the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by means of different methods and especially by means of the following methods: a) radical polymerization (usually under high pressure and at an 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, esters, amines, alkyls, alkenyls, cycloalkenyl, cyclopentadienyl, and / or aryls which may be both p- or s-coordinated. These metal complexes may have a free form or be supported on substrates, typically on activated magnesium chloride, titanium chloride (III), alumina or silicone oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or other activators can be used, typically metal alkyls, metal hydrides, alkyl metal halides, metal alkyl oxides or metal alkyloxanes, or compounds that give non-coordinating anions such as, for example, tris (pentafluorophenyl) boron, said metals are elements of groups la, lia and / or Illa of the Periodic Table. The activators can be I conveniently modified with other ester, ether, amine or silyl ether groups, these catalyst systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), CGCT constrained geometry catalyst technology (Dow), metallocene or single-site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example, PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example, LDPE / HDPE) . 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethereal / butyl copolymers 1-ene, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vini acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethyliane-norbornene; and blends of these copolymers with each other and with the polymers mentioned in 1) above, for example, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinylacetate (EVA) copolymers, LDPE / ethylene-acrylic acid (EEA) copolymers, LLDPE copolymers /EVE; LLDPE / EEA and random or alternating polyaikylene copolymers / carbon monoxide and their mixtures with other polymers for example, polyamides. 4. Hydrocarbon resins (eg, C5-Cg) including its hydrogenated modifications (eg, tackifiers) and mixtures of polyalkylenes and starch. 5. Polystyrene, poly-methylstyrene), poly (α-methylstyrene). 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact strength mixtures of the copolymers of styrene and of another polymer, for example, polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. 7. The graft copolymers of styrene or α-methylstyrene, for example, styrene on polybutadiene, styrene on polybicyclic-cslircno or copolymers of polybutadiene-acrylonitrile; styrene and acrylonitrile (methacrylonitrile) on polybutadiene; styrene acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as their mixtures with the copolymers listed in 6), for example, blends of copolymers known as ABS, MBS, ASA polymers or AES. 8. Halogen-containing polymers such as polychloroprene, chlorinated gums, chlorinated or sulfochlorinated polyethylene, chlorinated ethylene and ethylene copolymers, homo- and copolymers of epichlorohydrin, especially polymers of halogen-containing vinyl compounds, for example, polyvinyl, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride, as well as copolymers thereof, for example vinyl chloride / vinylidene chloride vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. i 9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified on impact with butyl acrylate. 11. Polymers derived from unsaturated alcohols and amines or from acyl derivatives or their acetals, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polylayl phthalate or melamine. polyallyl; as well as their copolymers with the olefins mentioned above in 1). 12. Homopolymers and copolymers of cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ether. 13. Polyacetals such as polyoxymethylene and 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 hydroxyl terminated polyethers, 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 diamines and dicarboxylic acids and / or aminocarboxylic acids 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-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or / and terephthalic acid and with or without an elastomer as a modifier, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforesaid 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). I 17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as copolyether esters of block derived from hydroxyl terminated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyether sulfones and polyether ketones. 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as, for example, phenol / I-foimaldehyde resins, urea / formaldehyde resins and molaminu / I formaldehyde bass. 22. Drying and drying non-drying alkyd resins. 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications of low flammability. 24. Crosslinkable acrylic resins derived from substituted acrylates, for example, epoxy acrylates, urethane acrylates or polyester acrylates. 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins. 26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides. 27. Natural polymers such as, for example, cellulose, gum, gelatin and chemically modified homologous derivatives thereof, for example, cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as, for example, methyl cellulose; as well as rosins and their derivatives. 28. Mixtures of the aforementioned polymers (polyblends), for example, PP / EPDM, polyamide / EPDM or ABS; PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO. 29. Synthetic natural organic materials that are compounds pure monomers or mixtures of these compounds, for example, oils minerals, animal or vegetable fats, oil 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 weight ratio, typically those used as spinning compositions, as well as the aqueous emulsions of these materials.

. Aqueous emulsions of natural or synthetic rubber, for example, natural latex or latexes of carboxylated styrene / butadiene copolymers. 31. Polysiloxanes, such as, for example, the hydrophilic polysiloxanes, mild I I described, for example, in U.S. Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Patent No. 4,335,147. 32. Polychethimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. Unsaturated acrylic resins include acrylates, polyether acrylates, cinyl or acryl copolymers with pendant unsaturated groups and acrylated melamines. Polychethimines are prepared from polyamines and ketones in the presence of an acid catalyst. 33. Compositions curable with radiation containing ethnically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer. 34. Epoxymelamine resins, such as, for example, light-stable epoxy resins crosslinked by means of a melamine resin with a high amount of functional epoxy coeterified solids, such as, for example, LSE-4103 (Monsanto). In general, the compounds of the present invention are used in between about 0.005 to about 5% by weight of the stabilized composition, although this may vary with the particular substrate and application. An advantageous range is between about 0.01 to about 3%, and especially between 0.05 to about 2%; the most preferred is the range between 0.05 to 1%. The stabilizers of the present invention can be rapidly incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of the articles formed. For example, the stabilizer can be mixed with the polymer in the form of dry powder, or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. The resulting stabilized compositions of the invention can optionally also contain between about 0.005% up to about 5%, preferably between about 0.01 or 0.025 to about 2%, and especially between about 0.1 to about 1% by weight of various conventional additives, such as, for example, the materials listed above, or mixtures thereof. 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- Ethyl phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohex) L) -4,6-dimethyl-phenyl, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-d? -tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched on the side chains, for example, 2,6 di non? l- methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenoi, 2,4-di-methyl -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-dioctithiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl- 4-nonylphenol. i 1.3. Hydroquinones and alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amiihydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroanisole, 2,5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 1.4 Tocopherols, for example, α-tocopherol, β-tocopherol, β-tocopherol, d-tocopherol and their mixtures (Vitamin E). 1.5 Hydroxylated thiodiphenyl ethers, for example, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert. butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4, -thiobis- (3,6-di-sec-amylphol), 4.4 '-bis (2,6-dimethyl-4-hydroxyphenyl!) disulfide. 1.6. Alkyl vandalis, for example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [ 4-Methyl-6- (a-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-melleylenbis (6-nonyl-4-methylphenol) , 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2 * -ethylenebis (4,6-di-tert-butylphenol), 2,2'-ethylilidenebis ( 6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis (6 - (- methylenebenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol ], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2- 1.7 O-, N- and S-benzyl compounds, for example , 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di- tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4- tert -butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5- di-tert-butyl-4-hydroxy- hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenoyl. 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-hydroxyanilin) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl) -4-hydroxyanilino) -1, 3,5-triazine, 2-octymercapto-4,6-bis (3,5-di-tert-butyl-4- i hydroxyphenoxy) -1, 3, 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-phenoxy) -1, 2,3-triazine, 1, 3,5-tris- (3,5- di-tert-butyl-4-hydroxy-benzyl) -isocyanurate, 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-buty-4-hydroxy-phenylethyl) -1, 3,5-triazine, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenyl) lpropionyl) -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, di-octadecyl-3,5-di-tert-butyl -4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester. 1.12. Acaminophenols. for example, 4-hydroxylauranyl, 4-hydroxysteatenyl, octyl- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. 1.13. Esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-monanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol , diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-tiapen adecanoi, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-trioxabicyclo [2.2.2] octane. 1.14. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6 hexanediol, 1, 9-nonanodium, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-triaoxabicyclo [2.2.2] octane. 1.15. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 9-nonanediol, ethylene diol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanide, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-osfa-2,6,7-trioxabvic [2.2.2] octane. 1.16. Esters of Sd-di-tert-buty-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2 -propanod? ol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1. 17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propionl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4) -hydroxy-phenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionl) -hydrazide, N, N'-bis [2- (3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard® XL-1 provided by Uniroyal). 1. 18. Ascorbic acid (Vitamin C) I 1.19. Amino antioxidants, for example, N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis- (1,4-dimethylpentyl) -p phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-! methylheptyl) -p-phenylenediane, N, N'-diclohex Lp-phenylenediamine, N-N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N - (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclonexyl-N'-phenyl- p-Phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N.N'-dimethyl-N.N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allildiphen-lamina, 4-isopropoxydiphenylamine, N-phenyl -1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example, p, p'-di-tert-octy diphenylamine, 4-n-butylaminophenol , 4-butyrylaminophen, 4-nonanoylaminophenol, 4-aodecanoylaminophenol, 4-octadecanoylaminophen, bis (4-methoxyphenyl) amine, '2,6-di-tert-butyl-4-d-methyl γ-methylene glycol, 2,4'-diaminodiphenylmethane, 1,4-diaminodiphenylmethane, N, N, N ', N'-telrammethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2- methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1'-3? -dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tert-octylamide , a mixture of dialkylated mono- and dialkyl-butyl / lerc-octyldiphenylamines, a mixture of mono- and dialkylated nonildiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of tert-butyldiphenylamines mono - and dialkylated, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of tert-butyl / tert-octylphenothiazines mono- and dialkized, a mixture of tert-octyl- mono and dialkylated phenothiazines, N-ailylphenothiazine, NNN, N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine , bis (2,2,6,6-tetramethylpiperid-4-yl) -secabate, 2,26,6-tetramethylpiperidin-4-one, 2,2,6, 6-tetramethylpiperidin-4-ol. 2. UV absorbers and light stabilizers! 2.1. 2- (2'-Hydroxyphenyl) benzotriazoles, for example, 2- (2'-hydroxy-5'-methylphenyl) -benzo-triazole, 2- (3 ', 5'-di-tert-butyl) 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenol) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1, 3,3- tetramethylbutyl) phenyl) benzothriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxy-phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2) '-hydroxy-5, -methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro- benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxypheni [) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-d1-tert-amyl-2'-hiaroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octylloxycarbonyl) phenyl) -5-chloro-benzotriazole 2- (3'-tert-butyl) -5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2- methoxycarbonylethyl) phenyl] -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-me Toxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxy-carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5, - [2 - (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3, -dodecyl-2, -hydroxy-5'-methylphenyl) benzotriazole, 2- (3 -'-tert-butyl-2) '-hydroxy-5' - (2-ioxoctylloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2-ylphenol ]; the product of the transesterification of 2- '-tert-butyl-5' - (2-methoxycarbonyl-ethyl) -2 -'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R- CH2CH2- COO- CH2CH2-] a- where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazoI-2-ylphenyl; 2- [2'-hydroxy-3 '- (a, a-dimethyl-benzyl) -5' - (1,1-, 3,3-tetramethylbutyl) -phenyl] benzotriazole; 2- [2'-hydroxy-3'- (1,1-, 3,3-tetramethylbutyl-5 '- (a, a-dimethylbenzyl) -phenyl] benzotriazole 2.2.2-Hydroxybenzophenones. for example, the derivatives of 4-methoxy-, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 40-trihydroxy and 2'-hydroxy-4,4'-dimethoxy. 2.3 Esters of substituted and unsubstituted benzoic acids, such as, for example, 4-tertiary butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4- di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy -benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate 2.4 Acrylates, for example, ethyl a-cyano-β, β-diphenylacrylate, isooctyl a-cinao-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy p-methoxycinnamate and N- (β-carbomethoxy- β-cyanovinyl) -2-methyIindoline. i | 2.5 Nickel compounds, for example nickel complexes of 2,2'-thio-bis- [4- (1, 1.SS-tetramethylbuty phenol], such as, for example, complex 1: 1 or 1: 2 with or without additional ligands such as, for example, n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, for example, methyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid ketoximes nickel complexes, for example 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional lysates 2.6 Space-hindered amines, for example , bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacato, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bs (1, 2.2 , 6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl) -4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (2-hydroxy-ethyl) -2,2,6,6-te Tramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N'-bis (2,2,6,6-tetramethyl-4-p) peridyl) hexamethylenediamine and 4-tert-octylamino-2,6 -dichloro-1, 3,5-triazine, tris (2) 2,6,6-tetramethyl-4-pperperidyl) nitrilotideacetate, tetrakis (2,2,6,6-tetramethyl-4-pyr) peridyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '- (1,2-ethanediol) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2 , 2,6,6-tetramethylpiperidine, 4-stearoxy-2,2,6,6-tetramethylpiperidine, bis (1, 2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2 - (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7J, 9,9-tetramethyl-1,3,8-triazaspiro [4,5] -decan-2,4 -dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidi) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensates of N, N ' -bis- (2,2,6,6-tetramethyl-4-pperperidol) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the 2-chloro-binder -4,6-bis (4-n-butylamino-2, 2,6,6-telramethylpiperidyl) -1, 3,5-riazine and 1,2-bis (3-am) inopylopylamino) elane, the condensate of 2-c-gold-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,4,5-triazine and 1, 2- bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, 3-dodecyl -1- (2,2,6,6-tetramethyl-4-pperidyl) pyrrolidin-2,5-dithonal 3-dodecyl-1- (1, 2,2,6,6-pentamethyl- 4-pperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a product of the condensation of N, N'-bis (2,2,6,6-tetramethyl-4-p? Peridyl) hexamethylenediamine and 4-cyclohexylamino-2,6- I dichloro-1,3,5-triazine, a product of the condensation of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,5-tetramethylpiperidine (CAS) Reg. Nr. [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-1-oxa-3,8 -diaza-4-oxo-spiro [4,5-decane, a product of the reaction of 7J, 9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-osospiro [4 , 5] decane and epichlorohydrin, 1, 1-bis (1, 2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis- formyl-N, N'-bis (2,2,6,6-te: rametl-4-pperidel) hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1, 2,2, 6,6, -pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxi-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, the product of the reaction of a maleic acid-α-olefin anhydride copolymer with 2,2,6,6-tetramethyl-4-aminopiperiaine or 1, 2,2,6,6-pentamethyl-4-aminopiperidine. 2.7. Oxamides for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dithoxy-5,5'-d, tert-butoxyanilide, 2,2'-didodecyloxy-5, 5'-di-tert-butoxyanilide, 2-ethoxy-2'-etioxyanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tcrc-butyl-2'-ctoxianiluiO and its mixtures with 2-ctoxy-2'-elyl-5, 4'-di-tert-butoxyanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8. 2- (2-hydroxyphenyl) -1, 3,5-triazines, for example, 2,4,6-tri (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2, (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxypheni) -4,6-bis- (4-methylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-) dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,5,5-triazine, 2- (2-hydroxy-4-! tridecyloxyphenyl-4,6-bis (2,4-d-methylphenyl)) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4I6-bs (2,4- dimethyl) -1, 3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-di- methylphenyl) -1,4,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyphenyl) -1 , 3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1, 3,5-triazine, 2- (2-hydroxy-4-methoxyphenin-4,6-diphenyl) -1, 3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) pheny1], 3,5-triazine, 2- (2-hydroxypheni) -4- (4- methoxyphenyl) -6-phenyl-1, 3,5-triazine, 2-. { 2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropylox] phenyl} 4,6-bis (2,4-dithmethenii) -1, 3,5-triazine. 3. Metal deactivators, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazine, sebacoyl bisphenylhydrazinda, N, N'-diacetyladipoyl hydrazide, N, N'- bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide. A. Phosphites and phosphonates, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, troctadecyl 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, diisodecyloxytentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenol) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol trifosphite, tetrakis (2) , 4, -di-tert-I butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz [d, g] -1, 3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1, 3,2-dioxafasforcin, bis (2,4-di) -tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2"-nitrile [triethyltris (3.3', 5,5'-tetra-tert-butii -1, 1 '-bifenI-2,2'-diyl) phosphite], 2-ethylhexyl (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2 , 2'-diyl) phosphite. Especially preferred are the following phosphites: Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168, Ciba-Geigy, tris (nonylphenyl) phosphite), octadecyl-alpha-hepadecyl-nitrone, N-hexadecyl-alpha-l leptadecyl-nitrile, N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hcxadecyl-nitrone , nitrone derived from N, N-dialkylhydroxylamine derived from amine hydrogenated. 7. Thiosynthetists, for example, dilauryl thiodipropionate or distearyl thiodipropionate. 8. Peroxide scavengers, for example, ß-thiodipropionic acid esters, for example, the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate. 9. Polyamide stabilizers, for example, copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts. 10. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, 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 piricatecholate. 11. Nucleating agents, for example, inorganic substances such as, for example, metal oxides such as, for example, titanium dioxide or magnesium oxide, phosphates, carbonates, or sulfates, preferably of alkaline earth metals; organic compounds such as, for example, mono- or polycarboxylic acids and their salts, for example, t-butyl-bromozoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as, for example, ionic copolymers (ionomers). 12. Carriers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, oxides of metals and hydroxides, carbon black, graphite, sawdust and flours and fibers of other natural products, synthetic fibers. 13. Other additives. for example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, fluid control agents, optical brighteners, flameproofing agents, antistatic agents, and blowing agents. 14. Benzofuranones and indolinones. for example, those described in U.S. Patent 4,325,863; U.S. Patent 4,338,244; U.S. Patent 5,175,312; U.S. Patent 5,216,052; U.S. Patent 5,252,643; DE-A-4316611; DE-A-4316622; DE-4316876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) -phenyl] -5,7-di-tert-butyl-benzof or ran-2-oha, 5, 7-d i -tert-butyl l-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] ] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethyphenyl) -5 , 7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- ( 3,4-dimethyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one .

| Other preferred compositions comprise, in addition to components (a) and (b) other additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers. The particularly preferred additives are the phenolic antioxidants (item 1 on the list), UV absorbers (items 2.1 and 2.2 of the list), spatially hindered amines (item 2.6 on the list), phosphite and phosphonites ( item 4 on the list) and hydroxylamines (item 6 on the list). Additional additives (stabilizers) which are also particularly preferred are benzo-furan-2-ones, for example, in US Patent No. 4,325,863, US-A-4,338,244 or US-A-5175312. UV absorbers of the benzotriazole class have a special value for combining with the compounds of the invention, for example, those listed above under 2.1, especially for the stabilization of synthetic organic polymers such as polyethylene or polypropylene. The UV absorber of particular interest is selected from the group consisting of 2- (2-hydroxy-3,5-di-a-cumylphenyl) -2H-benzotrazole.; 2- (2-hydroxy-5-methyl-1-phenyl) -2H-benzotriazoI; 2- (2-Hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole; 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-3,5-di-tert-amy1-phenyl) -2H-benzotriazoI; 2- (2-hydroxy-3-a-cumyl-5-tert-octylphenii) -2H-benzotriazole; 2,4-di-tert-butylphenyl 2,5-di-tert-butyl-4-hydroxybenzoate; 2-hydroxy-4-n-octyloxybenzophenone; 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine. Especially preferred are benzotriazoles such as, for example, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-ciorobenzotriazole; 1)) - The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocyanamate, neopentanotetrayl tetrakis (3,5-di-tert-butyl-4-) hydroxyhydrocyanamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (2,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1, 3,5-trimethyl-2,4,6-thirs (3,5-di-tert-butyl-4-) hydroxybenzyl) benzene, 3,6-dioxaoctametilen bis (3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis (4 , 6-di-tert-butylphenol), 1, 3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) -socyanurate, 1, 1, 3-tris (2- methyl-4-hydroxy-5-tert-butylphenyl) butane, 1, 3,5-tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoxy) ethyl] isocyanurate, 3,5-di - (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl) -4-hydroxyanillin) -3,5-di (octythio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), bis [3,3-] di (3-tert-butyl-4-hydroxyphenyl) butyrate] of ethylene, octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocin)? r) hydrazide, N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) -etl] -oxamide. The most preferred phenolic antioxidant is neopentanotetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1, 3,5-tritymethyl- 2,4,6-tris (3,5-di-tert-butyI-4-hydroxybenzyl) benzene, 1, 13,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis (4,6-di-tert-butylphenol). The hindered amine compound of particular interest is selected from the group consisting of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1, 2,2,6,6-pentamethylp peridin-4) -yl) sebacate, di (1, 2,2,6,6-pentamethylpiperidn-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl- 2,26,6-tetramethylpperidine, 4-stearoxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8- triaza-spiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-) oxopiperazin-4-yl) ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5.1.Jl 1.2] heneicosane, the product of the polycondensation of 2 , 4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), the product of the condensation of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the product of the polycondensation of 4,4, -hexamelílenbís- (amino-2,2,616-tetrametilpipieridina) and 1,2-dibr omoetano, tetrakis (2,2,6,6-tetramet piperidin-4-yl) -1, 2,3,4-butanetetracarboxylate, tetrakis (1, 2,2,6,6-pentamethylpiperidin-4-yl) 1, 2 , 3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4' I hexaetilenb¡s (amino-2,2,6,6-tetrametilpiperid¡na ), N, N ,, N "lN", - tetrakis [(4,6-bis (butyl-1, 2,2,6,6-pentamethyl-pyridin-4-yl) -amino-s-triazin -2-yl] -1, 10-diamino-4,7-diazadecane, [2,2,6,6-tetramethylpiperdin-4-yl / β, β, β ', β-tetramethyl- 3.9- (2,4,8,10-tetraoxaspiro [5.5] -undecane) diethyl] 1, 2,3,4-butanetetracarboxylate mixed, [1, 2,2,6,6-pentamethylpiperidin-4? L // ß, ß, ß ', ß'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecano) diethyl] 1, 2,3,4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-etiI-bisbis (2,2,6,6-tetramethylpiperazine- 3-on3), N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecyl succinimide, N- (1, 2,2,6,6-pentamethylpiperidin-4-yl) -n-dodecilsuccinim¡da, I N- (1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, 1-acetyl-3-dodeci! -7,7,9,9 -tetramethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione, di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di - (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, l-octyloxy ^^. d.d-tetramethyl ^ -hydroxy-piperidine, cop-. { [6-tert-octylamino-s-triazin-2,4-di-I] [2- (1-cyclohexyl-oxime-2,2,6,6-tetramethylpperiod-4-yl) Methyl-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino]} and 2,4,6-tris [N- (1-cyclohexy-oxy- 2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine. A most preferred hindered amine compound is bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1, 2,2,6,6-pentamethylpiperidin-4-yl) sebacate, dl (1, 2,2,6,6-pentamethylpiperidn-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, the product of the condensation of 1 - (2 -hydroxyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the product of the polycondensation 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4 ' -hexameti! enbis (amino-2,2,6,6-tetramethylpperidine), N, N ', N "; N"' - tetrakys [(4,6-bis (butyl)] -1 (1, 2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-triazine-2-yl] -, 10-diamino-4,7-diazadecane, di- (1-octyloxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyl-Ixo-2,2,6,6-tetramethylpiperi-n-4-yl) succinate, -octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly- {[6-t} ert-octylamino-s-triazin-2,4-d? l]] [ 2- (1-cyclohexyloxy-2, 2,6,6-I-tetramethyl-1-pyridin-4-yl) imino-hexamethylene- [4- (1-cyclohexyl-2, 2,6,6-tetramethyl) Peridin-4- il) ¡nno].}., or 2,4,6-tris [N- (1-c? clohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-but Lamino] -s-triazine, A stabilized composition according to the invention is of special importance, where component (a) is a thermoplastic olefin, and component (b) additionally contains an amine hindered NOR of low molecular weight. . Of particular interest is a stabilized composition according to the invention, wherein component (a) is an agricultural film that is exposed to pesticides, for example, pesticides containing halogen or sulfur; these compositions advantageously contain a metal stearate and zinc oxide as additional components. Also preferred is a stabilized composition according to the invention, wherein the component (a) is a polyolefin film, fiber, thick-section or thermoplastic olefin article that additionally contains a halogenated flame retardant such as decabromodium oxide. phenyl, ethylene bis- (tetrabromophthalimide), or ethylene bis- (dibromo-norbornanedicarboximide).

In the stabilized composition according to the invention, the component (a) can also be a paint-capable thermoplastic olefin (TPO). The present invention also relates to a process for preparing the present II mixture of N, N ', N "' - tris, 2,4-bis [(1-hydroxycarbyloxy-2,2,6,6-tetramethylpiperidin- 4-yl) alkylamino] -s-triazin-6-yl.} - 3,3'-ethylenedi-minodipropylamine; NIN ', N "-tris. { 2,4-bis [(1-hydroxycarbyloxy-2,2,6,6-tetra-methyl-piperidin-4-yl) alkylamino] -s-triazin-6-yl} -2,2'-ethylenediiminodipropylamine and its derivatives with puerue bond as described in formulas I, II, HA and III defined above comprising: reacting between two and four equivalents of 2,4-bis [(1 -hydroxycarbonyloxy-2,2,6,6-piperidin-4-yl) -butylamino] -6-chloro-s-triazine with an i equivalent of N, N'-bis (3 -aminopropyl) ethylenediamine. ! Preferably, the process includes reacting 2.5 to 3 equivalents of s-triazine with one amine equivalent; more preferably three equivalents of s-triazine to one equivalent of amine.

The tris-substituted compounds present have advantages over the related tetra-substituted compounds of the prior art. The binding reaction with the oxidation of the tert-butyl hydroperoxide used to introduce the 1-cyclohexyloxy or 1-octyloxy group into the hindered amine tetra-substituted s-triazine causes a significant chain scission of the resulting tetraamine portion in by-products of lower molecular weight. The cleavage of the chain is eliminated in the preparation of the present compounds because the group 1-alkoxy is introduced in the absence of the tetraamine backbone. The following examples are for illustrative purposes and were not prepared to limit the scope of the present invention in any way. Useful co-additives for use with the hindered amine compounds of formulas I, II, HA and III are the following: (IRGANOX® 1010, Ciba Specialty Chemicals Corp.); octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, (IRGANOXR 1076, Ciba Specialty Chemicals Corp.); } 1, 3,5-trimethyl-2,4,6-tris (2,5-di-tert-butyl-4-hydroxybenzyl) benzene, (IRGANOXR 1330, Ciba Specialty Chemicals Corp.); 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, (IRGANOX® 1024, Ciba Specialty Chemica Corp.); calcium [bis (monoethyl 3,5-ditert-butyl-4-hydroxybenzyl) phosphonate], I (lRGANOXR 1425, Ciba Specialty Chemicals Corp.); I.D.d-tris. S-di-tert-buiM-hydroxybenzyl) isocyanurate, (IRGANOXR 3114, Ciba Specialty Chemicals Corp.); 1, 3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl isocyanurate, (CYANOXR 1790, Cytec) Phosphorus compounds: tris (2,4-di-tert-butyl enyl) ) phosphite, (IRGAFOS ™ 168, Ciba Specialty Chemicals Corp.); bis (2,4-di-tert-butyl-6-methyl-phenyl) ethyl-phosphite, (IRGANOX® 38, Ciba Specialty Chemicals Corp.); , 2 ', 2"-nitriol [triethyl-tris- (3,3', 5,5'-tetra-tert-butyl-11, 1'-biphenyl-2,2'-diyl) phosphite], (IRGANOX® 12, Ciba Specialty Chemicals Corp.), tetrakis (2,4-di-butylphenyl) 4,4'-b-phenylenediphosphonite, (IRGAFOX® P-EPQ, Ciba Specialty Chemicals Corp.); nonylphenyl) phosphite, (TNPPR, General Electric), bis (2,4-di-tert-butynyl) pentaerythrityl diphosphite, (ULTRANOXR 626, General Electric); 2,2'-ethylidenebis (2,4-di-tert-butyl); butylphenyl) fluorophosphite, (ETANOX ^ 398, Ethyl Corp.) 2-Butyl-2-ethylpropan-1,3-diyl 2,4,6, -tri-tert-butylphenyl phosphite, (ULTRANOXR 641, General Electric). Benzofuran-2-ones: 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -2H-benzofuran-2-one, (HP-136R, Ciba Specialty Chemica ls Corp.). Hydroxylamines: N.N-dialkylhydroxylamine prepared by the dilecta oxidation of N, N-tallowamine di (hydrogenated), (FS-042R, Ciba Specialty Chemicals Corp.).

I hindered amines: b1s (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (T! NUV! NR 770, Ciba Specialty Chemicals Corp.); the polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, (TINUVIN® 622, Ciba Specialty Chemicals Corp.); N, N ', N ", N"' - tetrakis? 4,6-bis (butyl-1, 2,2,6,6-pentamethyl-4-yl) amino-s-triaz N-2-yl) -1,10-d-amino-4,7-diazadecane (CHIMASORBR 119, Ciba Specialty Chemicals Corp.); NOR hindered amines: bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN® 123, Ciba Specialty Chemicals Corp.); bis (1-octyloxy-2,2,6, '6-tetramethylpiperidin-4-yl) adipate; bis (1-cyclohexyloxy), 2,6,6-tetramethylpiperidin-4-yl) adipate; bis (1-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-cyclohexyloxy-2,2, i-3,6-tetramethylpiperidyl-4-octadecanoate. Flame retardants: Specialty Chemicals Corp.); 2- (2-hydroxy-3-a-cuml-5-tert-octylphenyl) -2H-benzotriazole, (TINUVIN® 928, Ciba Specialty Chemicals Corp.); 2,4-di-tert-butylphenyl 3,5-ditert-butyl-4-hydroxybenzoate, (TINUVIN® 120, Ciba Specialty Chemica, Corp.); 2,4-bis (2,4-dimethyphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-trizine, (CYASORBR 1164, Cytec). Example 1: 2-cORO-4,6-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butyl-amino] -s-triazine A mixture of 57.75 g (0.448 mol) of 70% aqueous tert-butylhydroperoxide, 250 ml of cyclohexane and 100 ml of a saturated sodium chloride solution was stirred vigorously and the organic layer was then separated and dried over anhydrous magnesium sulfate. The drying agent is removed by filtration, EL filtrate, 30.0 g (0.056 mol) of 2-cioro-4,6-bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine and 1.0 g of molybdenum trioxide were placed in a pressure bottle and heated to 130-140 ° C. The reaction mixture turned red rapidly and heating continued until the red color was discharged. The reaction mixture was allowed to cool and the solids were removed by filtration. The filtrate was concentrated under reduced pressure to give an oil which was purified by flash chromatography on silica gel to give 30.3 g (74% yield) of the title compound as a white crystal. Although the white crystal was essentially the title compound, a smaller amount of the bridged material was also present. Example 2: 2-Chloro-4,6-bis [N- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine stirred vigorously and the organic layer was then separated and dried over anhydrous magnesium sulfate. The drying agent was removed by filtration. Half of the solution of tert-butyl hydroperoxide / octane was combined with 30.0 g (0.056 mol) of 2-chloro-4,6-bis] N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -2-triazine and 1.0 g of molybdenum trioxide and the mixture was heated to reflux. The water was collected in a Dean-Stark trap. Once the sample turns red, it add the remaining tert-butyl hydroperoxide / octane solution during a . i period of three hours while the reaction mixture is maintained at Reflux. The mixture was heated for a period of four hours to discharge the red color. The reaction mixture was then cooled to room temperature to obtain an amber color which was purified by flash chromatography on silica gel (40: 1, heptane / ethyl acetate) to give 32.7 g (74% yield) of the title compound as a colorless syrup.

Although the colorless syrup is essentially the title compound, a small amount of bridged material was also present.

Example 3: Reaction of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-pyridin-4-yl) butylamino] -6-chloro-s-triazine with N, N'-bis (3-aminopropyl) ethyleneamine A mixture of 6.4 g (37 mmol) of N, N'-bis (3-aminopropyl) ethelene diamine, 107.6 g (147 mmol, 4.0 equivalent) of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -butyl] -6- chloro-s-triazine, as prepared in the Example 1, as a 70% solution in cyclohexane, and 31.0 g of a 20% aqueous sodium hydroxide solution were heated to 160 ° C for four hours. The reaction was cooled and diluted with 60 g of cyclohexane. The aqueous layer was stirred, the organic layer was concentrated and water was added to precipitate the crude product. The solids were washed with water until neutral and dried to give 102 g of the product. Analysis: Although four equivalents of 6-chloro-s-triazine were used for each equivalent of tetraamine, the NMR analysis showed that in average I only three triazinyl groups were attached to the main chain of I amine. The product is a mixture of isomers that include the bridged compounds. The mixture can be separated by means of preparation chromatography into pure components, particularly the two isomers of the formula without bridging described above. Example 4: Reaction of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine with N, N'-bis (3- aminopropyl) ethylenediamine The procedure of Example 3 was repeated, except that 3.0 equivalents of 2,4-bis [(1-cyclohexoxy-2,2,6,6-tetramethylpiperidin-4-yl) were used) butylamino] -6-chloro-s-triazine and the reaction was carried out at 120 ° C for nine hours. Again, the product is a mixture of isomers that include the bridged compounds. The NMR analysis showed that on average between 2.5 and three triazinyl groups were attached to the main chain of amine. The Tg for this product is 104-118UC measured by DSC.

Example 4a Comparative Example The compound of Example 62 of US Patent 5,204,473 is prepared by reacting the hindered amine precursor (CHIMASSORBR 905, Ciba), which has four substituted s-triazinyl groups appended to the 3.3 'backbone. ethylenediiminodipropylamine, with molybdenum trioxide and cyclohexane to form the corresponding 1-cid or hexyl oxy compound. This compound is supposedly tetrasubstituted based on the original CHIMASSORBR 905 starting material. However, the NMR and GPC analyzes indicate that under the reaction conditions the cleavage of the s-triazinyl groups and the formation of sub-! unknown colored products and that only two s-triazinyl groups can still be linked to the amine backbone. In order to distinguish the "trisubstituted" compound present in Example 4 from this prior art compound of Example 62 of US Patent 5,204,473, herein designated as Example 4a, the Tg of each compound is determined by DSC, and each compound undergoes the analyzes DSC and TGA. Compound of Example 4a 88-93 Example 4 104-118 DSC Analysis * Initial (° C) Peak (° C Example 4 Exolcrma 111 173 Exotherm 220 292 Example 4 Exotherm 228 228 Exotherm 269 299 TGA Analysis ** Temperature at 2% 10% 50% step loss (° C) Example 4a 171 260 321 Example 4 254 285 385 Scan * DSC (10 ° C / min up to 350 ° C, 100 ml / min N2, Al pots, ~ 10mg) DSC- Error estimate, Enthalpy up to + 10%, Temp up to + 2 ° C. ** TGA scan (10 ° C / min up to 500 ° C, 100 ml / min N2, Al pots, ~ 10mg) TGA - Error estimate, Temp up to ± 5 ° C, Weight up to ± 0.5% absolute.

Taking these data it becomes clear that the present compound of Example 4 prepared by means of a process different from the prior art compound of Example 62 of US Patent 5,204,473 is not the same material at all and that the compound present in Example 4 is more thermally stable than the prior art compound of Example 62. Example 5: Reaction of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6 -chloro-s-triazine with N, N'-bis (3-aminopiOpyl) ethylenediamine The procedure of Example 4 is repeated, except that 2,4-bis [(1-cyclohexyloxy-2) is used. , 2,6,6-tetramethylpperidin-4-yl) butylamino] -6-chloro-s-triazine.

This product is also a mixture of isomers that include the compounds with bridging. The average NMR analysis shows that between 2.5 to three triazinyl groups are attached to the main chain of the amine. The Tg of this product is between 109 - 116 ° C measured by DSC. Example 6: Reaction of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidn-4-yl) butylamino] -6-chloro-s-triazine with N, N'-bis (3-aminopropyl) ethylenediamine The procedure of Example 4 is repeated, except that 2.0 equivalents of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine were used. 4-1) butylamino] -6-chloro-s-triazine and the reaction was carried out at 120 ° C for five hours. The product is a mixture of isomers that include the compounds with linkage of puento. The NMR analysis shows that on average two triazinyl groups are linked to the main chain of the amine in the expected manner.

The Tg for this product is 101-114 ° C as measured by DSC. Example 7: Purification of the reaction product 2,4-bis [(1-cyclohexyloxy-2,2,6,6-pyridin-4-yl) butylamino] -6-chloro-s-triazine with N , N'-bis (3-aminopropyl) ethylenediamine A portion of the product mixture obtained in Example 4 was dissolved in toluene and passed through a Phenomenex ™ column (10 microns) with toluene as eluent. The fractions were collected and analyzed by gel permeation chromatography. The material having a molecular weight distribution consistent with the product was isolated by evaporation of the solvent. Example 8. Reaction of pure 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-) ii) butylamino] -6-chloro-s-triazine with N, N'- bis (3-aminopropyl) ethylene diamine Step 1 Tributyltin hydride was added to a solution of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and cyclohexyl iodide in chlorobenzene. The mixture was passed through silica gel with heptane / ethyl acetate to obtain 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one, which is free of any bis (4-) material. oxo-2,2,6,6-tetramethylpiperidm-l-yloxy) cyclohexane. Step 2 A mixture of the compound prepared in step 1 above, n-butylamine, methanol and a platinum catalyst on carbon 5% (50 psi, 25 ° C) was hydrogenated. The catalyst was removed by filtration, and the filtrate was evaporated to give 4-butylamino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine. Step 3 Two equivalents of the compound prepared in step 2 were added to a mixture of cyanuric chloride and xylene at 40 ° C. Sodium hydroxide was added, and the mixture was heated to 65 ° C to complete the reaction. The reaction mixture was cooled, water was added. The organic layer was washed with dilute acid, water, dried and evaporated to give 2,4-bis - [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) b? tilamino] -6-chloro-s-triazine.

By way of preparation, this intermediate is clearly not a mixture of compounds, as for example the case of the intermediate prepared in Example 1. Step 4. A mixture of N, N'-bis (3-aminopropyl) ethylene diamine and 3.0 equivalents of the compound prepared in step 3 was reacted according to the procedure in Example 4. Example 9: Reaction of 2,4-bis [(1-octyloxy) -2,2,6,6-piperidine -4-yl) butylamino] -I 6-chloro-s-triazine with N.N'-bis (3-aminopropyl) ethelene diamine A mixture of N, N'-bis (3-aminopropyl) ethelene diamine, 3 equivalents of 2,4-bis [(1-octyloxy-2,2,6,6-tetramethylpiperidn-4-yl) butylamino] -6-chloro-s-triazine prepared in Example 2 as an octane solution, and a 20% aqueous sodium hydroxide solution was heated to 120 ° C to complete the reaction. The reaction mixture was cooled, the organic layer was washed with water until neutral, and the solvent was evaporated to give the product mixture. The NMR analysis was consistent with the expected product of this reaction. Example 10. Reaction of 2,4-bis - [(! -methoxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine with N, N ' -bis (3-aminopropyl) ethylenediamine A mixture of N, N'-bis (3-aminopropyl) ethylenediamine, 3 equivalents of 2,4-bis [(1-methoxy-2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -6-cyoro-1, 3,5-triazine, a solution in cyclohexane, and a solution of sodium hydroxide! 20% aqueous was heated to 120 ° C until the reaction was complete. The reaction mixture was cooled, the organic layer was washed with water until neutral, and the solvent was evaporated to give the product mixture.

Example 11. Fiber-grade polypropylene, containing 0.05% by weight of calcium stearate and 0.05% by weight of hydroxylamine prepared by means of the direct oxidation of N, N-amine di (hydrogenated tallow) was mixed in dry with the test additives and then melt mixed at 234 ° C (450 ° F) in pellets. I The fully pelletized resin was then rotated at 246 ° C (425 I ° F) into a fiber using a Hills laboratory model fiber extruder. I The 41 filament spinning drag was stretched at a ratio of 1: 3.2 to give the final diner of 615/41. The stockings were woven with stabilized polypropylene fiber on a Lawson-Hemphill Analysis Weaving Machine and exposed to an Atlas Xenon-Act WeatherOmeter using SAE J 1885 with conditions for automotive interior of 89 ° C bpt, 0.55 kW / cm2 at 340 nm without spray cycle. The failure in this test was determined by observing the physical failure of the mean when p "scraped" with a blunt glass rod. The longer it takes for the fault to occur, the more effective the stabilizing system is. The control means that do not contain any of the present compounds fail after 200 hours of exposure while the average containing 0.25% by weight of the mixture of the compound present in Example 4 or containing 0.25% by weight of the compound of Example 3 fail after 700 hours of exposure. The average containing 0.5% by weight of the present compound of Example 4 fails after 1,000 hours, while the means with 0.75% by weight of the compound present of Example 4 have not failed after 1,000 hours of exposure. Example 12: Other propylene fiber stockings prepared as in Example 11 were exposed to a Blue M furnace at 120 ° C. The failure was determined by the criteria used in Example 11. The longer it takes for the failure to occur, the more effective the stabilizing system is. The stockings containing the present compounds exhibit good thermal stability efficiency. Example 13: Zero-grade polyethylene was mixed dry with approximately 1 D% by weight of the test additives and then melted at 200 ° C in "Masterbach" pellets. The "Masterbach" was mixed dry with polyethylene resin to obtain the desired concentration of the final stabilizer. This fully formulated stabilized resin was then blown at 200 ° C in a 150 micron thick film onto a DOLCI film line. The sop adas movies were exposed in a WeatherOmeter Atlas Xenon-ARC according to ASTM G26 at 65 ° C bpt, 0.35 W / rrr at 340 nm without spraying cycle. The films were periodically tested for any change in elongation using an Instron 1 12 strain gauge. Failure in this test was determined by observing the% elongation in the film. The films containing the mixture of the present compound show a good efficacy of light stability.

Example 14: The molded test specimens were prepared by injection molding of thermoplastic olefin pellets (TPO) containing a pigment, a phosphite, a phenolic antioxidant or hydroxylamine, a metal stearate, a UV absorber or a stabilizer. of amine hindered or hindered amine compounds of formulas I, II, HA and III; or a mixture of hindered amine and UV absorber. The pigmented TPO pellets were prepared from the pure pigment or from the pigment concentrate, stabilizers, co-additives and commercially available thermoplastic olefin by mixing the components in a single screw extruder Superior / MPM 1"with a general multi-purpose screw (24). :1 L / D) at 400 ° F (200 ° C), cooled in a water bath and the pellets were formed. The resulting formulated pellets were molded into 2"x 2" plates of 60 mil thickness (0.006 inches) at about 375 ° F (190 ° C) on a BOY 30M Injection Molding Machine. The pigmented TPO formulation composed of propylene mixed with a rubber modifier where the rubber modifier is a reacted polymer in situ or a blended product containing copolymers of propylene and ethylene with or without a ternary component such as for example ethylidene norbornene was stabilized with a base stabilization system consisting of an N, N-dialkylhydroxyamine or a mixture of hindered phenolic antioxidant and an organophosphorus compound. All the additive and concentration of pigment in the final formulations it is expressed as a percentage by weight based on the resin.

The test formulations contain thermoplastic olefin pellets and one or more of the following components: 0.0-0.2% pigment 0.0-50.0% talc 0.0-0.5% phosphite 0, 0 - 1, 25% phenolic antioxidant 0.0 - 0.1% hydroxylamine 0.0 - 0.5% calcium stearaxo 0.0 - 1, 25% UV absorbent 0.0 - 1, 25% stabilizer of hindered amine The components were dry mixed in a drum dryer prior to extrusion and molding. The test plates were mounted on metal structures and exposed to a WeatherOmeter Atlas Ci65 Xenon Arg 70 ° C temperature of a black panel, 0.55 W / m2 at 340 nm and 50% relative humidity with intermittent cycles of light / darkness according to the procedure of the Society of Automotive Engineers (SAE J 1960). The specimens were tested at intervals of approximately 625 kilojoules by performing color measurements on an Applied Color Systems spectrophotometer with the reflectance mode according to ASTM D 2244-79. The data collected includes the delta values E, L * a * and b *. The brightness measurements were carried out on a Opar-idad / Brightness Meter BYK-GARDNER at 60 ° according to ASTM D523.

UV exposure test - Test specimens exposed to UV radiation exhibit exceptional resistance to photodegradation when stabilized with light stabilizer systems formed by a combination of a benzotriazoi UV absorber and the hindered amine compounds of formula I , II, HA and III. The stabilized samples specifically show an improved gloss retention compared to prior art stabilizing systems. The resistance to color change after exposure to UV also improved. Polymeric blends containing an unsaturated ternary component, such as for example EPDM blends, especially show improved properties when stabilized by means of the present systems. In all cases, stabilized light formulations show greater resistance to photodegradation compared to unstabilized specimens that fail rapidly under UV exposure conditions as explained above.

Fully formulated resin was then blown at 200 ° C into a 150 micron thick film using a DOLCI film line. The resulting films were exposed to a greenhouse on a galvanized iron bra. The treatment includes applications of pesticides on a regular basis (eg, N-methyldithiocarbamate, VAPAMR every six months and SESMETRlNR every month). The performance was measured by monitoring the percentage residual elongation. The failure was defined as the time to 50% loss of the original elongation. The control film containing 0.4% by weight of the product of the polycondensation of 4,4'-hexamethylene-bs (amino-2,2,6,6-tetramethylpiperidine) and , 4-dichloro-6-tert-octylamino-s-triazine fails after an exposure of 160 Kilojoules in the 'greenhouse. The film containing 0.4% by weight of the present compound of Example 3 fails only after 300 kilojoules of exposure. These results show the resistance to pesticides of the present compounds of formula I, II, HA, and III. Example 15b: The master batch pellets as described in the Example 15a are mixed dry in a polyethylene resin to reach the final concentration of the stabilizer. The fully formulated resin was then blown at 200 ° C in a 25 micron film using a DOLCI film line. The resulting films are exposed to a floor to simulate the agricultural conditions of the films. The treatment includes exposure to a fumigatory substance of methyl bromide for the first few days at bOcj / rn. Performance was measured by monitoring time with respect to physical frailty.

The control containing 1.2% by weight of the product of the condensation of 4,4'-hexamethylene-bis (am'no-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6 -terc- II octylamino-s-triazine fails after an outside exposure of 70 kilojoules.

The film containing 1.2% by weight of the compound present in Example 3 is still intact after an exposure of 110 kilojoules. These results show the resistance of the present compounds of formula I, II, HA and III to the fumigating substances. Example 16: The greenhouse film samples were prepared in the manner described in Example 15, but in addition to the present compounds of the formula I, II, HA and III also contain metal stearate or metal oxide. Typical formulations contain between 0.05% to 2% by weight of the hindered amines present, between 0.05% to 0.5% of metal stearate such as, for example, calcium oxide, and among the 0 , 05% up to 0.5% of a metal oxide such as, for example, zinc oxide or magnesium oxide. The effectiveness was monitored in the manner described in Example 15. Films containing the amine amine compounds present exhibit good light stability. Example 17: The polypropylene fiber was prepared in the manner described in Example 11. In addition to the hindered amine compounds present in formulas I, II, IIA, and III, halogenated flame retardants selected in the formulation are also included. The flame retardants are tris (3-bromo-212-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromo-phthalimide), or ethylene bis- (dibromo-norbornanedicarboximide). Using the criteria for light stabilization described in Example 11, polypropylene fiber woven media containing the present hindered amines exhibit good light stability. Example 18: The molded grade polypropylene is dry mixed with the test additives and then mixed by melting into pellets. In addition, of the presently present hindered amine compounds of formulas I, II, HA and III, selected flame retardants are also included. The flame retardants are tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromophthalimide), or ethylene bis- (dibromo-norbornanedicarboximide). The fully pelletized resin is then injection molded into test specimens using a model Boy 50M laboratory injection molding machine. The test plates are mounted on metal structures and exposed on an Atlas Ci65 Xenon Are WeatherOmeter with intermittent cycles of dark light and sprayed with water following the ASTM G26 test procedure. The specimens are tested at periodic intervals in their changes in stress properties. The failure in this test is determined I by observing the loss of tension properties. I The longer it takes to lose the properties, the more effective the stabilizing system is. Test samples containing the amine amine compounds present exhibit good light stabilizing properties.

Example 19: The molded test specimens were prepared by injection molding of thermoplastic olefin pellets (TPO) as described in Example 14. In addition, of the hindered amines present of the formulas I, II, HA and III, also I flame retardants are included in the test specimens. The flame retardants are tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromophthalimide). or ethylene bis (dibromo-norbornanedicarboximide). Samples that include the hindered amines present exhibit a good light stabilizing activity. Example 20: The film grade polyethylene is formed and blown on a film at 200 ° C as described in Example 13 using a DOLCI film line. In addition, of the present hindered amines of formulas I, II, HA and III, they include flame retardants selected in the formulation. The flame retardants are tris (3-bromo-2,2-bis (bromomethyl) propyl) -phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromophthalimide) or ethylene bis- (dibromo-norbornanedicarboximide). When the light stabilizing activity was tested as described in Example 13, the films containing the hindered amines present exhibit good stabilization. Example 21: Molded test specimens were prepared by injection molding of thermoplastic olefin pellets (TPO) containing present amine compound compounds of formulas I; II, HA and III, pigments and other co-adylatives as deciphered in Example 14.

The test specimens were painted with one-pack paint systems and tested in the interactions between TPO / paint. Before painting, the test specimens were first rinsed with isopropanol and cleaned with air to remove dust. After a flash of five minutes, these specimens were coated with an adhesion promoter, then with a base coat, and then optionally with a clear coating. The typical film thickness of these various coatings is 0.1-0.3 millimeters for the adhesion promoter, 0.6-0.8 millimeters for the base coat, and 1.2-1.5 millimeters for the base coat. the clear coating. After painting, the specimens were cured in an oven at 120 ° C for 30 minutes.

The samples were tested to evaluate the TOP / paint interactions as follows: in the initial adhesion test, a clear cellophane adhesive tape is used to mask a 3 mm paint surface; in the humidity test, the painted plates are exposed for 240 hours at 38 ° C in an atmosphere that has 98% relative humidity. The blistering rate is tested in its visual observation in accordance with ASTM D 714. The samples containing amine amine compounds present exhibit good interaction properties between TPO / paint as determined with the above criterion. Example 22: Polyolefin resins including polypropylene, polyethylene homopolymer, polyolefin copolymer, or thermoplastic olefin (TPO) are dry mixed with the amine blocked compounds present of formulas I, II, HA and III and then Mix by melting in pellets. The resin completely formulated in pellets is then processed into a useful article such as, for example, extrusion into fibers, blowing or extrusion by molding into a film; blow molding in bottles; injection molding in molded articles; thermoformed in molded articles; extrusion in wires q cables for the home; or molded rotating in hollow articles. The materials containing the hindered amine compounds present exhibit a stability against the pernicious effects of exposure to light and thermal exposure. Example 23: The articles prepared according to Example 22 which additionally contain selected organic pigments as well as the present compounds of the formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure. Example 24: The articles prepared according to Example 22 which additionally contain an hindered phenolic antioxidant selected from the group consisting of neopentanotetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octadecyl 3,5-di-tert. -butyl-4-hydroxy-hydrocinnamate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinar? Oil) hydrazine, c [calcium bis (monoethyl 3,5-ditert-butyl-4-hydroxylbenzyl) phosphonate, 1, 3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 1, 3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate as well as the compounds present of formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure.

Example 25: The articles prepared according to Example 22 which additionally contain an organophosphorus stabilizer selected from the group consisting of tps (2,4-di-tert-butyl-phenyl) phosphite, bis (2,4-di-tert-di-tert. butyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2"-nitrile [triethyl-tris- (3,3', 5,5'-tetra-tert-butyl-1,1 '-bisphenyl-2 , 2'-düI) phosphite], tetrakis (2,4-di-butylphenyl) -4,4'-biphenylenediophosphine, tris (nonylphenyl) phosphine, bis (2,4-di-ter butylphenyl) pentaerythritol, diphosphite, 2,2'-ethylendibis (2,4-di-tert-butylphenyl) fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl-2,4,6-tri-tert. -butylphenyl phosphite as well as the present compounds of the formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure. Example 26: The articles prepared according to Example 22 additionally contain a benzofuranone stabilizer that is 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -2H-benzofuran-2-one, as well as as also the present compounds of the formulas I; II, HA and III also exhibit stability against the pernicious effects of UV light and thermal exposure. Example 27: The articles prepared according to Example 22 which additionally contain a dialkylhydroxylamine stabilizer which is N, N-dialkylhydroxylamine prepared by means of the direct oxidation of N, N-di (hydrogenated tallowamine) as well as the compounds present in Formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure. Example 28: Articles prepared according to Example 22 which additionally contain other obslanced amine stabilizers selected from the group consisting of b1s (2,2I6,6-tetramethyl-piperidin-4-yl) sebacate, the product of polycondensation of 1- (2-hydroxyethyl) -2,6,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N ', N ", N'" - tetrakis [4,6-bis (butl-1, 2,2,6,6-pentamethylpyridin-4-yl) amino-s-triazin-2-yl] -1,10-dimaino-4,7-diazadecane, the product of the polycondensation of 4.4 '-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine, the product of the polycondensation of 4,4'- hexa-methylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate, 3-dodecyl- 1- (1-acetyl-2,2,6,6-tetramethyl-piperidin-4-yl) -pyrrolidin-2,5-dione, 1, 3,5-trs. { N-cyclohexyl-N- [2- (2,2,6,6-tetramethyl-piperazin-3-one-4-yl) etii] amino} -s-triazine, poly. { methyl-3- (2,2,6,6-tetramethylpiperidin-4-ylox?) propyl] siloxane, the product of the condensation of 2,4-dichloro-6- (2,2,6,6- tetramethyl-piperidin-4-yl) butylamino) -s-triazine and 2,2'-ethylene-bis. { [2,4- (2,2,6,6-tetramethyl-pyridin-4-yl) butylamino-2-triazin-6-yl-aminotrimethylamino)} as well as the present compounds of the formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure. Example 29: The articles prepared according to Example 22 which additionally contain other N-hydrocarbyloxy substituted amines selected from the group consisting of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis ( 1-oCt-Ioxy-2,2,6,6-tetra-methylpiperidin-4-yl) adipate, bis (1-cyclohexyloxy-2,2, d, 6-tetramethylpiperidin-4-yl) adipate, bis ( 1-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate and 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate as well as also the compounds present in the Formulas I, II, HA and III also exhibit stability against the pernicious effects of actinic light and thermal exposure. Example 30: Articles prepared according to Example 22 which additionally contain a UV absorber of o-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or an o-hydroxyphenyl-s-triazine selected from the group consisting of 2- (2- hydroxy-3,5-di-a-cumylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3), 5-di-tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylfeniI) -2H-benzotriazole, 2- (2-hydro? I-3-a-cumyl) -5-tert-octyphenyi) -2H-benzotriazole, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-hydroxy-4-n-octyloxybenzophenone and 2, 4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octylphenyl) -s-triazine as well as also the present compounds of formulas I, II, HA and III also exhibit stability against the effects pernicious of UV light and thermal exposure. All times in which it is mentioned in the specification or claims, the portion of the formula: refers to a 2,2,6,6-tetramethylpiperidyl residue (linked at positions 1 and 4).

Claims (7)

1. A composition stabilized against thermal, oxidative or light-induced degradation comprising: (a) an organic material prone to degradation, oxidant or induced by light and, (b) a mixture of NIN'lN '"- tris. {2,4-bis [(1-hydroxycarbinoxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-trizain-6-yl} -3,3'-ethylenediiminodipropylamine; N, N ', N' "- tris. { 2,4-bis [(1-hydrocarbyloxy-2,6,6,6-tetramethylpiperid [n-4-yl] aminoquin] -s-triazin-6-yl} -3,3'- ethylenediiminodipropylamine and bridging derivatives as described with formulas I, II, HA and III RiNH-CHzCHaCHz RzCHaCHzNRaCHzCHzCHzNHR-, (I)

T-E, -T, di)

I HAVE)

G-E.-GrE-j-Gz (lll) where E is

Ei is and where in the tetraamine of the formula I, Ri and R2 are the E portion of s-triazine; and one of R3 and R4 is the portion E of s-triazine with the other being R3 and R4 hydrogen, R is methyl, cyclohexyl or octyl, R5 is alkyl of 1 to 12 carbon atoms, where in the compound of formula II or HA when R is cyclohexyl or octyl, T and Ti are each tetraamine substituted by R1-R4 as defined in formula I, wherein (1) one of the E-portions of s-triazine in each tetraamine is replaced by the E1 group aue forms a bridge between the two T and Ti tetraamines, or (2) the group R1 can be both terms in the same tetraamine T as i in the formula IIA where two of the E portions of the tetraamine are I replaced by a group Ei, or (3) all three substituents of s-triazine of tetraamine T can be E1 in such a way that E1 binds to T and Ti and a second E1 has both terms in telraamine T, L is cyclohexanodii or u octanodullo; where in the compound of formula III G, G? and G2 are each tetraamines substituted by R1-R4 as defined for formula I, except that G and G2 each have one of the s-triazine portions replaced by E ?, and G1 has two of the triazine E portions replaced by Ei, in such a way that there is a bridge between G and G1 and a second bridge between G1 and G2. 2. A composition according to claim 1 wherein the organic material (component a) is a natural, semi-synthetic or synthetic polymer, especially a polyolefin. 3. A composition according to claim 1 wherein in portions E and E1 of the compounds of component (b), R is cyclohexyl or octyl, and R5 is butyl. 4. A composition according to claim 1 wherein the component (b) is contained in an amount between 0.005 to 5% by weight of the stabilized composition. 5. A composition according to claim 1 which additionally contains an effective stabilizing amount of at least one co-additive stabilizer selected from the group consisting of the phenolic antioxidants, 2- (2'-hydroxy-phenyl) -benzotrazoles, hydroxyphenyl -s-triazines, metal stearates, metal oxides, organophosphorus compounds, furanone antioxidants, hydroxylamines, spatially hindered amines and their mixtures.

6. A composition according to Claim 2 wherein the component (a) is a polyolefin that is exposed to pesticides or contains a halogenated flame retardant.

7. A mixture of N, N ', N "' - tris. {2,4-bis [(1-hydroxycarbyloxy-2,2,6,6-tetramethylpiperidn-4-y! l) alkylamino] -s-trizain-6-yl.} - 3, 3'-etlenediiminodipropylamine; N, N ', N ", - tr, s. { 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine and bridged-link derivatives as described with formulas I, II, HA and III RINH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (I) Ei is where in the tetraamine of the formula I, R? and R2 are the E portion of s-triazine, and one of R3 and R4 is the E portion of s-triazine, the other being R3 and R4 hydrogen, R is methyl, cyclohexyl, or octyl, R5 is alkyl of 1 to 12 carbon atoms, wherein in the compound of formula II or HA when R is cyclohexyl or octyl, T and Ti are each a tetraamine substituted by R1-R4 as defined in formula I, where (1) one of the E-portions of s-triazine in each tetraamine is! replaced by the group Ei, which forms a bridge between the two tetraamines T and Ti, or (2) the group E1 can have both terms in the same tetraamine T as in the formula HA where two of the E portions of the tetraamine are replaced for a group Ei, or (3) all three s-triazine substituents of tetraamine T can be E1 so that Ei binds to T and Ti and a second E1 has both terms in tetraamine T, L is cyclohexanediylp or octanediyl; wherein in the compound of the formula III G, Gi and G2 are each tetraamines substituted by R1-R4 as defined in formula I, except that G and G2 each have the S-triazine portions E replaced by Ei, and G1 has two of the E-portions of triazine butylamino] -2-tr'a'zin-6-yl} -3,3'-ethylenediiminodipropylamine; c) N, N ', N' "- tris., 2,4-bis [(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -2 -triazin-6-yl.) .3,3'-etlendiminodipropylamine; d) N, N'lN "-tris. { 2,4-bis [(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazin-6-yl] -3,3 '-ethilendi¡m¡nod¡prop¡lam¡na; e) N, N ', N' "- L rs { 2,4-bis [(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamine] - s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine; f) N, N ', N "-tris. { 2,4-bis [(1-methoxy-2,2,6,6-tetramethyl-1-pyridin-4-yl) n-butylamino] -s-triazin-6-yl} -3,3'-ethylenediminodipropylamine.