DE19964603B4 - Sterically hindered amine ethers and their use as stabilizers for organic material - Google Patents

Abstract

A composition comprising A) an organic polymer sensitive to oxidative degradation, thermal degradation and / or degradation by actinic radiation, and B) at least one compound of formulas IIIa, IVa or Va ...

Description

The invention relates to sterically hindered amine ethers, their use as stabilizers for organic material against degradation by light, oxygen and / or heat and corresponding compositions.

A variety of publications describe the stabilization of organic material using spe

hindered amine (HALS) compounds as stabilizers. A valuable class of sterically hindered amines are compounds in which the nitrogen atom is part of a heterocyclic ring and the nitrogen atom carries another organic substituent attached via an oxygen atom (NOR-HALS, Kurumada et al., J. Polym. Poly. Chem. Ed. 22, 277-81 (1984); US-A-5,204,473 ); the oxygen-bonded substituent is introduced into these compounds by etherification of the free oxyl or hydroxylamine with suitable agents.

Some N-allyl nitroxides rearrange to amine ethers under certain conditions (Meisenheimer rearrangement; Chem. Ber. 52, 1667 (1919); Chem. Ber. 55, 513 (1922)). Cleavage of the nitroxide to form alkene and hydroxylamine (Cope elimination) is a competing reaction that increases in speed with increasing steric hindrance (March, Advanced Organic Chemistry, IV. Edition, Wiley, 1992).

worin
R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen;
R₅, R₆, R₇, R₈ und R₉ unabhängig voneinander H, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen und R₇ und R₈ zusammen ebenfalls eine chemische Bindung bilden können; und
R eine organische verbindende Gruppe, die 2-500 Kohlenstoffatome enthält, darstellt und zusammen mit den Kohlenstoffatomen, an die sie direkt gebunden ist, und dem Stickstoffatom eine substituierte 5-, 6- oder 7-gliedrige, cyclische Ringstruktur bildet; wobei R vorzugsweise ein C₂-C₅₀₀-Kohlenwasserstoff ist, der gegebenenfalls 1-200 Heteroatome, ausgewählt aus Stickstoff, Sauerstoff, Phosphor, Schwefel, Silicium und Halogen, enthält, und
dadurch gekennzeichnet, daß eine Verbindung der Formel II

worin alle Reste R und R₁–R₉ wie in Formel I definiert sind, oxidiert wird.It has now surprisingly been found that the oxidation of a 1-allyl-substituted, sterically hindered amine leads effectively to the corresponding 1-allyloxy-substituted product. The invention therefore relates to a process for the preparation of a compound of the formula I.

wherein
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, and R ₇ and R ₈ together can also form a chemical bond; and
R represents an organic linking group containing 2-500 carbon atoms and together with the carbon atoms to which it is directly attached and the nitrogen atom forms a substituted 5-, 6- or 7-membered cyclic ring structure; wherein R is preferably a C ₂ -C ₅₀₀ hydrocarbon optionally containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen, and
characterized in that a compound of the formula II

wherein all of R and R ₁ -R _{9 are} as defined in formula I is oxidized.

R ₇ and R ₈ , as a chemical bond, together form an allene double bond in formula I and a triple bond in formula II.

In the compounds of formula I and II and further products R _1, R _2, R ₃ and R ₄ are each independently preferably methyl or ethyl, especially methyl.

R ₅ , R ₆ , R ₇ , R ₈ and R ₉ , as an electron-attracting group, include -CN, nitro, halo or -COOR ₁₀ , wherein R _{10 is} C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ Cycloalkyl, C ₇ -C ₉ phenylalkyl or phenyl. Preferred as an electron-attracting group are -CN or -COOR ₁₀ , wherein R _{10 is} C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl, in particular wherein R _{10 is} C ₁ -C ₁₂ alkyl or cyclohexyl ,

R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are preferably, independently of one another, H or methyl, in particular H. Also preferred are compounds in which R ₅ and R ₆ independently of one another represent H or methyl, in particular H, and R ₇ , R ₈ and R ₉ independently of one another are haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ or R ₇ and R ₈ together form a chemical bond.

Further preferences for the linking group R are described below mainly for products of the formulas III, IV and V.

Of particular importance is a process for the preparation of a compound of formula I by oxidation of a compound of formula II wherein
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, an electron-withdrawing group, C ₆ -C ₁₂ -aryl substituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, and
R is a C ₃ -C ₅₀₀ hydrocarbon radical optionally containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, and forms together with the two carbon atoms and the nitrogen atom a substituted 6-membered cyclic ring structure ,

Aryl stands for a group that meets the Debye-Hueckel rule; preferred as C ₆ -C ₁₂ aryl are phenyl and naphthyl.

Alkyl is a branched or unbranched radical which, within the given definitions, is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 , 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3 Trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , Eicosyl or docosyl.

Alkanoyl is alkyl joined via a carbonyl bond; thus, C ₂ -C ₂₀ alkanoyl includes acetyl, propionyl, butyryl, hexanoyl, stearoyl.

Haloalkyl is alkyl which is substituted by halogen, for example 1 or 2 halogen atoms. Halogen atoms are preferably chlorine or bromine, in particular bromine.

Cycloalkyl is a saturated, monovalent, monocyclic hydrocarbon radical, for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl; preferred is cyclohexyl.

Organic radicals or hydrocarbons containing heteroatoms such as alkyl or alkylene interrupted by hetero groups such as oxygen or NH usually contain these heteroatoms as typical functional groups such as oxo, oxa, hydroxy, carboxy, ester, amino, amido, nitro, Nitrilo, isocyanato, fluorine, chlorine, bromine, phosphate, phosphonate, phosphite, silyl, thio, sulfide, sulfinyl, sulfo, heterocyclyl, including pyrrolyl, indyl, carbazolyl, furyl, benzofuryl, thiophenyl, benzothiophenyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl , Pyrimidinyl, pyrazinyl, triazolyl, benzotriazolyl, triazinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and correspondingly saturated and / or substituted groups such as piperidyl, piperazinyl, morpholinyl, etc. They may be interrupted by one or more of these groups; usually there are no O-O, O-N (other than nitro, cyanato, isocyanato, nitroso or as the group N-O within a group of formula I 'below), N-N (except in heterocyclic ring structures), N-P or P-P regardless of the order.

Preferably, in heteroatom-containing organic radicals or hydrocarbons such as R, there is no more than one heteroatom attached to the same carbon atom through a single bond. A spacer consisting of one or more heteroatoms is usually embedded in a carbon chain or ring or inserted into a carbon-hydrogen bond.

The compounds of the formula I can be monomeric or polymeric. They contain one or more groups of the formula I '

When the compounds of formula I 'are polymeric, they may contain a group of formula I' in the repeating structural unit.

Starting compounds of the formula II are known in the art or can be obtained in analogy to known compounds. The present process may start from isolated compounds of formula II or may employ the solution of these starting compounds obtained immediately after the synthesis.

In the process of the invention, the oxidation reaction can be carried out using known oxidizing agents, for example oxygen, peroxides or other oxidizing agents, such as nitrates, permanganates, chlorates, with peroxides, such as hydrogen peroxide-based systems, especially peracids, such as perbenzoic acid or peracetic acid are. The oxidizing agent is suitably used in a stoichiometric amount or in excess, for example, using 1-2 moles of active oxygen atoms for each group of formula I 'in the desired product.

The reaction may be carried out in the presence of a suitable solvent, for example an aromatic or aliphatic hydrocarbon, alcohol, ester, amide, ether or halogenated hydrocarbon; Examples are benzene, toluene, xylene, mesitylene, methanol, ethanol, propanol, butanol, dimethylformamide, dimethyl sulfoxide, methylene chloride; preferred is a C ₁ -C ₄ -alcohol, benzene, toluene, xylene or chlorinated C ₁ -C ₆ -hydrocarbon.

Temperature and pressure are not critical and depend mainly on the oxidant system used; preferably the temperature during the reaction is maintained in the range between -20 ° C and + 40 ° C. Suitably, the pressure is maintained near atmospheric pressure, for example between 0.5 and 1.5 bar; when the oxidation is carried out with gaseous oxygen, the oxygen or oxygen / inert gas pressure may exceed the atmospheric pressure.

The process according to the invention can be followed by further process steps known in the art, for example hydrogenation of an ethylenic double bond, halogenation, for example bromination, of an ethylenic double bond and / or polymerization, with or without previous isolation of the product of formula I.

The hydrogenation of the ethylenic double bond (carbon-carbon double bond) in the compound of formula I can be achieved by methods known in the art, for example reaction with gaseous hydrogen under catalytic conditions or reaction with hydrogenating agents. Preferred is the catalytic hydrogenation; known catalysts, such as Pt, Pd, Ni, Ru, Rh, on supports, such as carbon, or without supports, Raney nickel, etc., can be used.

worin R, R₁–R₆ und R₉ wie vorstehend definiert sind.The hydrogenation of an allenic double bond in a compound of formula I, wherein R ₇ and R ₈ together represent a chemical bond, proceeds in 2 steps. The first step results in a partially hydrogenated product which can be isolated or subjected to further derivatization and which corresponds to the formula IV,

wherein R, R ₁ -R ₆ and R _{9 are} as defined above.

worin R, R₁–R₆ und R₉ wie vorstehend für Formel I definiert sind und R₇ und R₈ H, C₁-C₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen.Complete hydrogenation gives a product of formula III

in which R, R ₁ -R ₆ and R _{9 are} as defined above for formula I and R ₇ and R _{8 are} H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron-attracting group or C ₆ -C ₁₂ -aryl which is substituted by a radical selected from C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, represent.

The halogenation is another subsequent reaction which can be carried out subsequent to the process of the present invention, principally according to methods known in the art and using the appropriate reactant as described, for example, in J. March, Advanced Organic Chemistry: Reaction Mechanisms and Structure, 4th Edition, Wiley, 1992, page 812, summarized. Halogen is thereby added to the carbon-carbon double bond of a compound of formula I or IV to give an α, β-dihalogenated product. The halogen reagent X ₂ , wherein X is F, Cl, Br, I or preferably Cl or Br, in particular Br, can be used in gaseous, liquid or solid form, pure or as a solution. Halogen may also be released during the reaction in suitable amounts using a suitable carrier or source.

The reactions can be carried out according to methods known in the art using hydrogen pressures in the usual range, preferably between 0.5 and about 200 bar, in particular between 1 and 100 bar (1 bar = 10 ⁵ Pa). The reactions can be carried out using suitable solvents, for example water, hydrocarbons, such as hexane, petroleum ether fractions, toluene, xylene, esters, ethers, halogenated hydrocarbons or alcohols, such as methanol or ethanol. The reactions can also be carried out without a solvent. The temperatures are not critical and are mainly in the range between -10 ° C and about 150 ° C, for example between 0 ° C and the boiling point of the solvent, such as in the range of 0-100 ° C or 20-80 ° C.

worin R, R₁, R₂, R₃ und R₄, R₅, R₆ und R₉ wie in Anspruch 1 für Formel I definiert sind,
R₇ und R₈ H, C₁-C₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, Halogen, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen; und
beide Reste R₂₀ und R₂₁ entweder Wasserstoff oder Halogen darstellen, dadurch gekennzeichnet, daß eine Verbindung der Formel II oxidiert wird und das erhaltene Zwischenprodukt der Formel I Hydrierung und/oder Halogenierung unterzogen wird.The present invention therefore relates to a process for the preparation of a compound of the formula V

wherein R, R ₁ , R ₂ , R ₃ and R ₄ , R ₅ , R ₆ and R _{9 are} as defined in claim 1 for formula I,
R ₇ and R _{8 are} H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, halogen, an electron-attracting group or C ₆ - C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; and
both radicals R ₂₀ and R _{21 are} either hydrogen or halogen, characterized in that a compound of formula II is oxidized and the resulting intermediate of formula I is subjected to hydrogenation and / or halogenation.

The above process can also be carried out in a manner in which the intermediate of formula I is derivatized to a further structure of formula I prior to its hydrogenation and / or halogenation, for example by esterification, dimerization, trimerization or polymerization, or wherein the intermediate of the formula I first hydrogenated and then further derivatized, for example by esterification, dimerization, trimerization or polymerization.

Preferred is a process for the preparation of a compound of formula V, wherein
R represents an organic linking group containing 2-500 carbon atoms and, together with the carbon atoms to which it is directly attached, forming the nitrogen atom a substituted, 5-, 6- or 7-membered cyclic ring structure;
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
R ₅ , R ₆ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron-attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;
R ₇ and R _{8 are} H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, halogen, an electron-attracting group or C ₆ - C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, and both of R ₂₀ and R _{21 are} either hydrogen or halogen.

The particularly preferred products of the process according to the invention have the formulas IIIc, IVa and Va described below.

In general, all products of the process according to the invention can be used as stabilizers for organic material against damaging effects of light, oxygen and heat. Of particular value are the compounds of formulas I, Ia, III, IV and V. The best results are achieved with compounds of formula III wherein
R, R ₁ , R ₂ , R ₃ and R _{4 are} as defined for formula I and
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H. C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, CN, COOR ₁₀ , in which R ₁₀ as defined for formula I, or C ₆ -C ₁₂ -aryl which is substituted by a radical selected from C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy. The most effectively stabilized organic material by the present compounds is organic polymeric material described below, for example, coatings and thermoplastic bulk polymers, films or fibers. When the polymers come into contact with a pesticide, such as a pesticide containing sulfur and / or halogen atoms, the products of the present process achieve both stabilization against light and the harmful effects of the pesticide. This is especially important for polymers such as films, tapes or fibers used in agriculture, mainly polyolefins such as PE or PP, or polyolefin copolymers. Preferred compounds of the invention are those of the formula III, in particular of the following formula IIIc.

An important application for all products of the present process is the stabilization of paper and pulp, especially paper or pulp that still contains lignin, against yellowing. The application of the present products may be carried out as described, for example, in International Patent Application No. WO98 / 04381 and corresponding US patent application Ser. 09/119567 and the publications cited therein. Most preferred for this application is the use of a monomeric compound of formula III, for example a compound wherein R is C ₃ -C ₁₂ -alkylene or C ₄ -C ₁₂ -alkylene, interrupted by O, NH, OCO or NHCO, R ₁ -R _{4 is} methyl or ethyl, in particular methyl, and R ₅ -R _{9 are} each H or C ₁ -C ₄ -alkyl, in particular H; Examples are 1-propyloxy-2,2,6,6-tetramethylpiperidine, 1-propyloxy-2,2,6,6-tetramethylpiperidin-4-one or the product of the present Example 4a (see below).

Furthermore, the products of the process of the invention can be advantageously used as a flame retardant for organic polymers. Thus, using the products of the invention, an organic polymer is stabilized against the damaging effects of light, oxygen and heat, while at the same time effectively reducing the flammability of the polymer. The application of the present products can be carried out as described, for example, in International Patent Application no. WO98 / 13469 and corresponding US patent application Ser. 09/104718 described and the publications cited therein and in EP-A-792 911 or US-A-5,393,812 be executed. Most preferred for this application the use of a compound of formula III or V, in particular those of the following formula IIIc, or Formula V. wherein at least one of the radicals R _5, R _6, R _7, R _8, R _9, R ₂₀ or R _{21 represents} halogen, in particular bromine. The instant compounds may be used as flame retardants, alone or in combination with known flame retardants, such as a flame retardant compound selected from the halogenated, phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrates and metal oxides, or mixtures thereof.

It is a further result of this invention that some compounds of formula III are particularly well suited as stabilizers for organic material against the damaging effects of light, oxygen and heat.

• A) ein organisches Polymer, das gegen oxidativen Abbau, thermischen Abbau und/oder Abbau durch aktinische Strahlung empfindlich ist, und
• B) mindestens eine Verbindung der Formeln IIIa, IVa oder Va
  
  worin R' und R jeweils eine organische verbindende Gruppe der Formel
  
  darstellen; E₂ -CO- oder -(CH₂)_p- darstellt, worin p 0, 1 oder 2 ist; E₁ ein Kohlenstoffatom, das die zwei Reste R₂₄ und R₂₅ trägt, darstellt, oder >N-R₂₅ ist oder Sauerstoff ist und R₂₄ und R₂₅ Wasserstoff oder einen organischen Rest darstellen, dadurch gekennzeichnet, daß die verbindende Gruppe R insgesamt 2-500 Kohlenstoffatome enthält und mit den Kohlenstoffatomen, an die sie direkt gebunden ist, und dem Stickstoffatom eine substituierte 5-, 6,- oder 7-gliedrige cyclischen Ringstruktur bildet; R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen; R₅, R₆, R₇, R₈ und R₉ unabhängig voneinander H, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen; R₂₀ und R₂₁ Halogen darstellen und R₂₂ und R₂₃ Wasserstoff darstellen oder zusammen eine chemische Bindung darstellen.

The invention therefore also provides compositions comprising

• A) an organic polymer that is sensitive to oxidative degradation, thermal degradation and / or degradation by actinic radiation, and
• B) at least one compound of the formulas IIIa, IVa or Va
  
  wherein R 'and R each represents an organic linking group of the formula
  
  group; E _{2 is} -CO- or - (CH ₂ ) _p - wherein p is 0, 1 or 2; E _{1 represents} a carbon atom bearing the two radicals R ₂₄ and R ₂₅ , or> NR ₂₅ or oxygen and R ₂₄ and R _{25 represent} hydrogen or an organic radical, characterized in that the linking group R contains a total of 2-500 carbon atoms and with the carbon atoms to which it is directly attached and the nitrogen atom forms a substituted 5-, 6-, or 7-membered cyclic ring structure; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; R ₂₀ and R _{21 are} halogen and R ₂₂ and R _{23 are} hydrogen or together represent a chemical bond.

worin R₂₄ und R₂₅ zusammen =O darstellen, oder worin R₂₄ Wasserstoff darstellt und R₂₅ Wasserstoff oder Hydroxy darstellt.Usually R 'in formula IIIa is not a linking group

wherein R ₂₄ and R ₂₅ together represent = O, or wherein R _{24 represents} hydrogen and R _{25 represents} hydrogen or hydroxy.

Preferred is a formula IIIa, wherein R 'represents C ₇ -C ₅₀₀ -hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, and together with the two carbon atoms and the nitrogen atom, a substituted, Forms a 5- or 6-membered cyclic ring structure and
R ₁ , R ₂ , R ₃ and R _{4 are} as defined above.

The present invention further provides the use of the compounds of formula IIIa for stabilizing organic polymers against oxidative, thermal or actinic radiation induced degradation. The invention also includes a process for stabilizing organic polymers against thermal, oxidative and / or actinic radiation degradation, which comprises adding at least one compound of formula IIIa to the polymer.

worin
n₁ eine Zahl von 1 bis 4 ist, G und G₁ unabhängig voneinander Wasserstoff oder Methyl darstellen,
G₁₁ n-Propoxy, O-CH=C=CH₂, O-CH=CH-CH₃ oder halogeniertes n-Propoxy, insbesondere n-Propoxy oder bromiertes n-Propoxy, darstellt;
G₁₂, wenn n₁ 1 ist, C₁-C₁₈-Alkyl, das nicht unterbrochen oder durch ein oder mehrere Sauerstoffatome unterbrochen ist, Cyanoethyl, Benzoyl, Glycidyl, einen einwertigen Rest von einer aliphatischen, cycloaliphatischen, araliphatischen, ungesättigten oder aromatischen Carbonsäure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen einwertigen Silylrest, vorzugsweise einen Rest von einer aliphatischen Carbonsäure mit 2 bis 18 Kohlenstoffatomen oder von einer cycloaliphatischen Carbonsäure mit 7 bis 15 Kohlenstoffatomen oder von einer α,β-ungesättigten Carbonsäure mit 3 bis 5 Kohlenstoffatomen oder von einer aromatischen Carbonsäure mit 7 bis 15 Kohlenstoffatomen darstellt, wobei jede Carbonsäure in der aliphatischen, cycloaliphatischen oder aromatischen Einheit mit 1 bis 3 Gruppen -COOZ₁₂, worin Z₁₂ H, C₁-C₂₀-Alkyl, C₃-C₁₂-Alkenyl, C₅-C₇-Cycloalkyl, Phenyl oder Benzyl bedeutet, substituiert sein kann;
G₁₂, wenn n_l 2 ist, C₂-C₁₂-Alkylen, C₄-C₁₂-Alkenylen, Xylylen, einen zweiwertigen Rest von einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, vorzugsweise einen Rest von einer aliphatischen Dicarbonsäure mit 2 bis 36 Kohlenstoffatomen oder von einer cycloaliphatischen oder aromatischen Dicarbonsäure mit 8-14 Kohlenstoffatomen oder von einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbaminsäure mit 8-14 Kohlenstoffatomen darstellt, wobei jede Dicarbonsäure in der aliphatischen, cycloaliphatischen oder aromatischen Einheit mit einer oder zwei Gruppen -COOZ₁₂ substituiert sein kann;
G₁₂, wenn n₁ 3 ist, einen dreiwertigen Rest von einer aliphatischen, cycloaliphatischen oder aromatischen Tricarbonsäure, die in der aliphatischen, cycloaliphatischen oder aromatischen Einheit mit -COOZ₁₂ substituiert sein kann, von einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure darstellt oder einen dreiwertigen Silylrest darstellt;
und G₁₂, wenn n₁ 4 ist, einen vierwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure darstellt.Specific examples of sterically hindered amines are described below under classes (a ') to (j'). (a ') A compound of the formula (1a)

wherein
n _{1 is} a number from 1 to 4, G and G ₁ independently of one another represent hydrogen or methyl,
G _{11 is} n-propoxy, O-CH = C = CH ₂ , O-CH = CH-CH ₃ or halogenated n-propoxy, especially n-propoxy or brominated n-propoxy;
G ₁₂ , when n _{1 is} 1, C ₁ -C ₁₈ -alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid Acid containing carbamic acid or phosphorus or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms or of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms or of an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of one represents aromatic carboxylic acid having 7 to 15 carbon atoms, wherein each carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety having 1 to 3 groups -COOZ ₁₂ wherein Z _{12 is} H, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl;
G ₁₂ , when n _{l is} 2, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical , preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms or of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, wherein each dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety may be substituted with one or two groups -COOZ ₁₂ ;
G ₁₂ , when n is ₁ , represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety with -COOZ ₁₂ , of an aromatic tricarbamic acid or a phosphorus-containing acid, or a trivalent silyl group;
and G ₁₂ , when n _{1 is} 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

In any case, the abovementioned carboxylic acid radicals are radicals of the formula (-CO) _x R, where x is defined as n ₁ and the meaning of R is given by the definition given above.

Alkyl having up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-butyl Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Examples of various radicals G ₁₂ are given below.

When G _{12 is} a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl radical ,

For example, when G _{12 is} a monovalent silyl radical, it is a radical of the formula - (C _j H _2j ) -Si (Z ') ₂ Z''wherein j is an integer in the range of 2 to 5 and Z' and Z '' independently of one another represent C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy.

When G _{12 is} a divalent radical of a dicarboxylic acid, it is for example a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl (3 , 5-di-tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptendicarbonyl radical or a group of the formula

When G _{12 is} a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.

When G _{12 is} a tetravalent radical of a tetracarboxylic acid, it is, for example, a tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

When G _{12 is} a divalent radical of a dicarbamic acid, it is, for example, a hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

worin G und G₁ unabhängig voneinander Wasserstoff oder Methyl darstellen,
G₁₁ n-Propoxy darstellt,
G₁₃ Wasserstoff, C₁-C₁₂-Alkyl, C₂-C₅-Hydroxyalkyl, C₅-C₇-Cycloalkyl, C₇-C₈-Aralkyl, C₁-C₁₈-Alkanoyl, C₃-C₅-Alkenoyl, Benzoyl oder eine Gruppe der Formel (1b-1)

darstellt,
n₂ die Zahl 1, 2 oder 3 ist;
und G₁₄, wenn n₂ 1 ist, Wasserstoff, C₁-C₁₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₇-Cycloalkyl, C₁-C₄-Alkyl, das mit einer Hydroxyl-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiert ist, Glycidyl, eine Gruppe der Formel -CH₂-CH(OH)-Z oder der Formel -CONH-Z, worin Z Wasserstoff, Methyl oder Phenyl bedeutet, darstellt;
G₁₄, wenn n₂ 2 ist, C₂-C₁₂-Alkylen, C₆-C₁₂-Arylen, Xylylen, eine Gruppe -CH₂-CH(OH)-CH₂ oder eine Gruppe -CH₂-CH(OH)-CH₂-O-D-O-, worin D C₂-C₁₀-Alkylen, C₆-C₁₅-Arylen, C₆-C₁₂-Cycloalkylen bedeutet, darstellt, oder, mit der Maßgabe, daß G₁₃ nicht Alkanoyl, Alkenoyl oder Benzoyl darstellt, G₁₄ alternativ 1-Oxo-C₂-C₁₂-alkylen, einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure oder alternativ die Gruppe -CO- darstellen kann,
G₁₄, wenn n₂ 3 ist, eine Gruppe

darstellt, oder, wenn n₂ 1 ist, G₁₃ und G₁₄ zusammen einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure darstellen können. Preference is given to compounds of the formula (1a) in which G and G _{1 represent} hydrogen, G _{11 represents} hydrogen or methyl, n _{1 represents} 2 and G _{12 represents} the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms. (b ') A compound of the formula (1b)

wherein G and G ₁ independently of one another represent hydrogen or methyl,
G _{11 represents} n-propoxy,
G _{13 is} hydrogen, C ₁ -C ₁₂ -alkyl, C ₂ -C ₅ -hydroxyalkyl, C ₅ -C ₇ -cycloalkyl, C ₇ -C ₈ -aralkyl, C ₁ -C ₁₈ -alkanoyl, C ₃ -C ₅ - Alkenoyl, benzoyl or a group of formula (1b-1)

represents,
n _{2 is} the number 1, 2 or 3;
and G ₁₄ , when n is ₂ , is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, C ₁ -C ₄ alkyl which is hydroxyl, Cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CH ₂ -CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl;
G ₁₄ , when n _{2 is} 2, C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, a group -CH ₂ -CH (OH) -CH ₂ or a group -CH ₂ -CH (OH ) -CH ₂ -ODO-, wherein DC is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₅ -arylene, C ₆ -C ₁₂ -cycloalkylene, or, provided that G _{13 is} not alkanoyl, alkenoyl or Benzoyl, G _{14 may} alternatively be 1-oxo-C ₂ -C ₁₂ -alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or alternatively may represent the group -CO-,
G ₁₄ , if n _{2 is} 3, a group

or when n is ₂ , G ₁₃ and G _{14 may} together represent a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Some examples of the radicals G ₁₃ , G ₁₄ and D are given below.

Alkyl substituents are as defined above for (a ').

C ₅ -C ₇ -cycloalkyl substituents are in particular cyclohexyl.

G ₁₃ as C ₇ -C ₈ -aralkyl is in particular phenylethyl or in particular benzyl.

G ₁₃ as C ₂ -C ₅ -hydroxyalkyl is in particular 2-hydroxyethyl or 2-hydroxypropyl.

G ₁₃ as C ₁ -C ₁₈ alkanoyl is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and G ₁₃ as C ₃ -C ₅ alkenoyl is in particular acryloyl.

G ₁₄ as C ₂ -C ₈ alkenyl is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

G ₁₄ as hydroxyl, cyano, alkoxycarbonyl or carbamide-substituted C ₁ -C ₄ -alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl ) ethyl.

C ₂ -C ₁₂ -alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C ₆ -C ₁₅ -arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C ₆ -C ₁₂ cycloalkylene is in particular cyclohexylene.

G ₁₄ as 1-oxo-C ₂ -C ₁₂ alkylene is preferably a group

darstellt und G₁₄, wenn n₂ = 1, Wasserstoff oder C₁-C₁₂-Alkyl darstellt, und wenn n₂ = 2, C₂-C₈-Alkylen oder 1-Oxo-C₂-C₈-alkylen darstellt. (c') Eine Verbindung der Formel (1c)

worin n₃ die Zahl 1 oder 2 ist, G, G₁ und G₁₁ wie unter (b') definiert sind und G₁₅, wenn n₃ 1 ist, C₂-C₈-Alkylen, C₂-C₈-Hydroxyalkylen oder C₄-C₂₂-Acyloxyalkylen darstellen, und wenn n₃ 2 ist, G₁₅ die Gruppe (-CH₂)₂C(CH₂-)₂ darstellt.Preference is given to compounds of the formula (1b) in which n _{2 is} 1 or 2, G and G _{1 are} hydrogen, G _{13 is} hydrogen, C ₁ -C ₁₂ -alkyl or a group of the formula

and G ₁₄ , when n ₂ = 1, is hydrogen or C ₁ -C ₁₂ alkyl, and when n _{2 is} 2, C ₂ -C ₈ alkylene or 1-oxo-C ₂ -C ₈ alkylene. (c ') A compound of the formula (1c)

wherein n _{3 is} the number 1 or 2, G, G ₁ and G _{11 are} as defined under (b ') and G ₁₅ , when n _{3 is} 1, C ₂ -C ₈ alkylene, C ₂ -C ₈ hydroxyalkylene or C ₄ -C ₂₂ acyloxyalkylene, and when n _{3 is} 2, G _{15 is} the group (-CH ₂ ) ₂ C (CH ₂ -) ₂ .

worin n₄ die Zahl 1 oder 2 ist, G, G₁ und G₁₁ wie unter (b') definiert sind,
G₁₆ Wasserstoff, C₁-C₁₂-Alkyl, Allyl, Benzyl, Glycidyl oder C₂-C₆-Alkoxyalkyl darstellt, und
G₁₇, wenn n₄ 1 ist, Wasserstoff, C₁-C₁₂-Alkyl, C₃-C₅-Alkenyl, C₇-C₉-Aralkyl, C₅-C₇-Cycloalkyl, C₂-C₄-Hydroxyalkyl, C₂-C₆-Alkoxyalkyl, C₆-C₁₀-Aryl, Glycidyl oder eine Gruppe der Formel -(CH₂)_p-COO-Q oder -(CH₂)_p-O-CO-Q darstellt, worin p 1 oder 2 ist und Q C₁-C₄-Alkyl oder Phenyl darstellt, und
G₁₇, wenn n 2 ist, C₂-C₁₂-Alkylen, C₄-C₁₂-Alkenylen, C₆-C₁₂-Arylen, eine Gruppe der Formel -CH₂-CH(OH)-CH₂-O-D'-O-CH₂-CH(OH)-CH₂- darstellt, worin D' C₂-C₁₀-Alkylen, C₆-C₁₅-Arylen, C₆-C₁₂-Cycloalkylen oder eine Gruppe der Formel -CH₂CH(OD'')CH₂-(OCH₂-CH(OD'')CH₂)₂- darstellt, worin D'' Wasserstoff, C₁-C₁₈-Alkyl, Allyl, Benzyl, C₂-C₁₂-Alkanoyl oder Benzoyl darstellt,
T₁ und T₂ unabhängig voneinander Wasserstoff, C₁-C₁₈-Alkyl oder unsubstituiertes oder Halogen- oder C₁-C₄-Alkylsubstituiertes C₆-C₁₀-Aryl oder C₇-C₉-Aralkyl darstellen oder
T₁ und T₂ zusammen mit dem Kohlenstoffatom, an das sie binden, einen C₅-C₁₄-Cycloalkanring bilden. G ₁₅ as C ₂ -C ₈ -alkylene or C ₂ -C ₈ -hydroxyalkylene is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene. G ₁₅ as C ₄ -C ₂₂ acyloxyalkylene is, for example, 2-ethyl-2-acetoxymethylpropylene. (d ') A compound of formula (1d-1), (1d-2) or (1d-3),

wherein n _{4 is} the number 1 or 2, G, G ₁ and G _{11 are} as defined under (b '),
G _{16 is} hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl, and
G ₁₇ , when n _{4 is} 1, is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl , C ₂ -C ₆ alkoxyalkyl, C ₆ -C ₁₀ aryl, glycidyl or a group of the formula - (CH ₂ ) _p -COO-Q or - (CH ₂ ) _p -O-CO-Q, wherein p Is 1 or 2 and Q is C ₁ -C ₄ alkyl or phenyl, and
G ₁₇ , when n is 2, C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkenylene, C ₆ -C ₁₂ -arylene, a group of the formula -CH ₂ -CH (OH) -CH ₂ -O- D'-O-CH ₂ -CH (OH) -CH ₂ -, wherein D 'is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₅ -arylene, C ₆ -C ₁₂ -cycloalkylene or a group of the formula - CH ₂ CH (OD '') CH ₂ - (OCH ₂ -CH (OD '') CH ₂ ) ₂ - wherein D '' is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C _{12 is} alkanoyl or benzoyl,
T ₁ and T ₂ independently of one another represent hydrogen, C ₁ -C ₁₈ -alkyl or unsubstituted or halogen or C ₁ -C ₄ -alkyl-substituted C ₆ -C ₁₀ -aryl or C ₇ -C ₉ -aralkyl or
T ₁ and T ₂ together with the carbon atom to which they bind form a C ₅ -C ₁₄ cycloalkane ring.

A compound of formula (1d-3) is preferred.

Some examples of various variables of formulas (1d-1), (1d-2) and (1d-3) are given below.

C ₁ -C ₁₂ -alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n Undecyl or n-dodecyl.

C ₁ -C ₁₈ -alkyl substituents may be, for example, the groups mentioned above and additionally for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C ₂ -C ₆ -alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

G ₁₇ as C ₃ -C ₅ alkenyl is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

G ₁₇ , T ₁ and T ₂ as C ₇ -C ₉ -aralkyl are in particular phenethyl or, in particular, benzyl. When T ₁ and T ₂ together with the carbon atom form a cycloalkane ring, this may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

G ₁₇ as C ₂ -C ₄ -hydroxyalkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

G ₁₇ , T ₁ and T ₂ as C ₆ -C ₁₀ -aryl are in particular phenyl or α- or β-naphthyl which are unsubstituted or substituted by halogen or C ₁ -C ₄ -alkyl.

G ₁₇ as C ₂ -C ₁₂ -alkylene is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

G ₁₇ as C ₄ -C ₁₂ -alkenylene is in particular 2-butenylene, 2-pentenylene or 3-hexenylene.

G ₁₇ as C ₆ -C ₁₂ -arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

D '' as C ₂ -C ₁₂ alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

worin n₅ die Zahl 1 oder 2 ist und G₁₈ eine Gruppe der Formel

darstellt, worin G und G₁₁ wie unter (b') definiert sind und G₁ und G₂ Wasserstoff, Methyl darstellen oder zusammen einen Substituenten =O darstellen,
E -O- oder -ND'''- darstellt,
A C₂-C₆-Alkylen oder -(CH₂)₃-O- darstellt und x₁ die Zahl 0 oder 1 ist,
D''' Wasserstoff, C₁-C₁₂-Alkyl, C₂-C₅-Hydroxyalkyl oder C₅-C₇-Cycloalkyl darstellt,
G₁₉ mit G₁₈ identisch ist oder eine der Gruppen -N(G₂₁)(G₂₂), -OG₂₃, -N(H)(CH₂OG₂₃) oder -N(CH₂OG₂₃)₂ darstellt,
G₂₀, wenn n = 1, mit G₁₈ oder G₁₉ identisch ist, und wenn n = 2, eine Gruppe -E-D^IV-E- darstellt, worin D^IV C₂-C₈-Alkylen oder C₂-C₈-Alkylen, das durch 1 oder 2 Gruppen -NG₂₁-unterbrochen ist, darstellt,
G₂₁ C₁-C₁₂-Alkyl, Cyclohexyl, Benzyl oder C₁-C₄-Hydroxyalkyl oder eine Gruppe der Formel

darstellt,
G₂₂ C₁-C₁₂-Alkyl, Cyclohexyl, Benzyl oder C₁-C₄-Hydroxyalkyl darstellt und G₂₃ Wasserstoff, C₁-C₁₂-Alkyl oder Phenyl darstellt oder G₂₁ und G₂₂ zusammen C₄-C₅-Alkylen oder C₄-C₅-Oxaalkylen, beispielsweise -CH₂CH₂-O-CH₂CH₂- oder eine Gruppe der Formel -CH₂CH₂-N(G₁₁)-CH₂CH₂- darstellen.For example, D 'as C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene has one of the definitions given for D under (b'). (e ') A compound of the formula (1e)

wherein n _{5 is} the number 1 or 2 and G _{18 is} a group of the formula

wherein G and G _{11 are} as defined under (b ') and G ₁ and G _{2 are} hydrogen, methyl or together represent a substituent = O,
E -O- or -ND '''- represents,
Is AC ₂ -C ₆ -alkylene or - (CH ₂ ) ₃ -O- and x _{1 is} the number 0 or 1,
D '''is hydrogen, C ₁ -C ₁₂ -alkyl, C ₂ -C ₅ -hydroxyalkyl or C ₅ -C ₇ -cycloalkyl,
G _{19 is} identical to G ₁₈ or represents one of the groups -N (G ₂₁ ) (G ₂₂ ), -OG ₂₃ , -N (H) (CH ₂ OG ₂₃ ) or -N (CH ₂ OG ₂₃ ) ₂ ,
G ₂₀ , when n = 1, is identical to G ₁₈ or G ₁₉ , and when n = 2, represents a group -ED ^IV -E-, wherein D ^{IV is} C ₂ -C ₈ -alkylene or C ₂ -C ₈ - Alkylene, which is interrupted by 1 or 2 groups -NG ₂₁ , represents
G _{21 is} C ₁ -C ₁₂ -alkyl, cyclohexyl, benzyl or C ₁ -C ₄ -hydroxyalkyl or a group of the formula

represents,
G _{22 is} C ₁ -C ₁₂ -alkyl, cyclohexyl, benzyl or C ₁ -C ₄ -hydroxyalkyl and G _{23 is} hydrogen, C ₁ -C ₁₂ -alkyl or phenyl or G ₂₁ and G ₂₂ together are C ₄ -C ₅ - Alkylene or C ₄ -C ₅ -oxaalkylene, for example -CH ₂ CH ₂ -O-CH ₂ CH ₂ - or a group of the formula -CH ₂ CH ₂ -N (G ₁₁ ) -CH ₂ CH ₂ - represent.

Some examples of the various variables in the formula (1e) are given below.

C ₁ -C ₁₂ -alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n Undecyl or n-dodecyl.

Hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C ₅ -C ₇ -cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

C ₂ -C ₆ -alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

When G ₂₁ and G ₂₂ together represent C ₄ -C ₅ -alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

(f') Eine Verbindung der Formel (1f)

worin G₁₁ wie unter (b') definiert ist.Examples of polyalkylpiperidine compounds of this class are the compounds of the following formulas:

(f ') A compound of the formula (1f)

wherein G _{11 is} as defined under (b ').

(g ') Oligomeric or polymeric compounds whose recurring structural unit contains a 2,2,6,6-Tetraalkylpiperidinylrest, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and copolymers thereof containing such radicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds of this class are the compounds of the following formulas, wherein n is a number from 2 to about 200, preferably 2 to 100, e.g. 2 to 50, 2 to 40 or 3 to 40 or 4 to 10.

The meanings of the end groups that saturate the free valencies in the oligomeric or polymeric compounds listed below depend on the method used to prepare the compounds. The end groups can also be modified after the synthesis of the compounds.

worin der Index n im Bereich von 1 bis 15, insbesondere im Bereich 3 bis 9, liegt;
R₁₂ C₂-C₁₂-Alkylen, C₄-C₁₂-Alkenylen, C₅-C₇-Cycloalkylen, C₅-C₇-Cycloalkylendi(C₁-C₄-alkylen), C₁-C₄-Alkylendi(C₅-C₇-cycloalkylen), Phenylendi(C₁-C₄-alkylen) oder C₄-C₁₂-Alkylen, unterbrochen durch 1,4-Piperazindiyl, -O- oder >N-X₁, wobei X₁ C₁-C₁₂-Acyl oder (C₁-C₁₂-Alkoxy)carbonyl bedeutet, darstellt oder eine der nachstehend für R₁₄ angegebenen Definitionen, mit Ausnahme von Wasserstoff, aufweist; oder R₁₂ eine Gruppe der Formel (Ib') oder (Ic') darstellt,

X₂ C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Phenyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist, darstellt; und
die Reste X₃ unabhängig voneinander C₂-C₁₂-Alkylen darstellen;
die Reste B unabhängig voneinander Cl, -OR₁₃, -N(R₁₄)(R₁₅) oder eine Gruppe der Formel (IIId) darstellen;

R₁₃, R₁₄ und R₁₅, die gleich oder verschieden voneinander sind, Wasserstoff, C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist, C₃-C₁₈-Alkenyl, Phenyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Tetrahydrofurfuryl oder C₂-C₄-Alkyl, das in der 2-, 3- oder 4-Stellung mit -OH, C₁-C₈-Alkoxy, Di(C₁-C₄-alkyl)amino oder einer Gruppe der Formel (Ie') substituiert ist;

wobei Y -O-, -CH₂-, -CH₂CH₂- oder >N-CH₃ bedeutet, darstellt,
oder -N(R₁₄)(R₁₅) zusätzlich eine Gruppe der Formel (Ie') darstellt;
X -O- oder >N-R₁₆ darstellt;
R₁₆ Wasserstoff, C₁-C₁₈-Alkyl, C₃-C₁₈-Alkenyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Tetrahydrofurfuryl, eine Gruppe der Formel (IIIf)

oder C₂-C₄-Alkyl, das in der 2-, 3- oder 4-Stellung mit -OH, C₁-C₈-Alkoxy, Di(C_i-C₄-alkyl)amino oder einer Gruppe der Formel (Ie') substituiert ist, darstellt;
R₁₁ eine der für R₁₆ angegebenen Definitionen aufweist.Examples are compounds of the formula (1g-1)

wherein the index n is in the range of 1 to 15, in particular in the range 3 to 9;
R _{12 is} C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkenylene, C ₅ -C ₇ -cycloalkylene, C ₅ -C ₇ -cycloalkylenedi (C ₁ -C ₄ -alkylene), C ₁ -C ₄ -alkylenedi (C ₅ -C ₇ -cycloalkylene), phenylenedio (C ₁ -C ₄ -alkylene) or C ₄ -C ₁₂ -alkylene interrupted by 1,4-piperazinediyl, -O- or> NX ₁ , where X _{1 is} C ₁ C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl, or has one of the definitions given below for R ₁₄ , except for hydrogen; or R _{12 represents} a group of the formula (Ib ') or (Ic'),

X _{2 is} C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; Phenyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; and
the radicals X ₃ independently of one another represent C ₂ -C ₁₂ -alkylene;
the radicals B independently of one another represent Cl, -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of the formula (IIId);

R ₁₃ , R ₁₄ and R ₁₅ , which are the same or different from each other, are hydrogen, C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl substituted, C ₃ -C ₁₈ alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or C ₂ -C ₄ alkyl which is in the 2-, 3- or 4-position with -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (Ie ') is substituted;

where Y is -O-, -CH ₂ -, -CH ₂ CH ₂ - or> N-CH ₃ ,
or -N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie ');
X represents -O- or> NR ₁₆ ;
R _{16 is} hydrogen, C ₁ -C ₁₈ -alkyl, C ₃ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (IIIf)

or C ₂ -C ₄ alkyl in the 2, 3 or 4 position by -OH, C ₁ -C ₈ alkoxy, di (C _i -C ₄ alkyl) amino or a group of the formula ( Ie ') is substituted;
R _{11 has} one of the definitions given for R ₁₆ .

sein und die an die Diaminogruppe gebundene Endgruppe kann beispielsweise Wasserstoff oder eine mit B disubstituierte Triazinylgruppe, wie eine Gruppe

sein.In these compounds, the end group attached to the triazine residue may be, for example, a group B or -N (R ₁₁ ) -R ₁₂ -B, such as chlorine, or a group

and the end group attached to the diamino group may be, for example, hydrogen or a triazinyl group disubstituted with B, such as a group

be.

darstellt.It may be appropriate to replace the chlorine atom attached to the triazine, for example by a group -OH or amino. Suitable amino groups are in general: pyrrolidin-1-yl, morpholino, -NH ₂ , -N (C ₁ -C ₈ -alkyl) ₂ and -NY '(C ₁ -C ₈ -alkyl), wherein Y' is hydrogen or a Group of formula

represents.

worin n₆ die Zahl 1 oder 2 ist, G und G₁₁ wie unter (a') definiert sind und G₁₄ wie unter (b') definiert ist. (i') Eine Verbindung der Formel (1i)

worin die Reste G₃₉ unabhängig voneinander eine Gruppe der Formel (1i-1)

darstellen, worin G₄₀ C₁-C₁₂-Alkyl oder C₅-C₁₂-Cycloalkyl darstellt, G₄₁ C₂-C₁₂-Alkylen darstellt und G₄₂ Wasserstoff, C₁-C₈-Alkyl, -O-, -CH₂CN, C₃-C₆-Alkenyl, C₇-C₉-Phenylalkyl, C₇-C₉-Phenylalkyl, das am Phenylrest mit C₁-C₄-Alkyl substituiert ist, oder C₁-C₈-Acyl darstellt.In the oligomeric and polymeric compounds shown above, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3- Trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Eicosyl or docosyl;
Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
an example of C ₇ -C ₉ phenylalkyl is benzyl and
Examples of alkyls are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. (h ') A compound of the formula (1h)

wherein n _{6 is} the number 1 or 2, G and G _{11 are} as defined under (a ') and G _{14 is} as defined under (b'). (i ') A compound of the formula (1i)

in which the radicals G _{39 are} independently of one another a group of the formula (1i-1)

in which G _{40 is} C ₁ -C ₁₂ -alkyl or C ₅ -C ₁₂ -cycloalkyl, G _{41 is} C ₂ -C ₁₂ -alkylene and G _{42 is} hydrogen, C ₁ -C ₈ -alkyl, -O-, - CH ₂ CN, C ₃ -C ₆ -alkenyl, C ₇ -C ₉ -phenylalkyl, C ₇ -C ₉ -phenylalkyl which is substituted on the phenyl radical by C ₁ -C ₄ -alkyl, or C ₁ -C ₈ -acyl represents.

Alkyl is, for example, C ₁ -C ₄ -alkyl, in particular methyl, ethyl, propyl or butyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is, for example, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.

Alkenyl is preferably allyl.

Phenylalkyl is preferably benzyl.

Acyl is preferably acetyl.

worin
die Reste A unabhängig voneinander -OR₁₃, -N(R₁₄)(R₁₅) oder eine Gruppe der Formel (IIId) darstellen;

X -O- oder >N-R₁₆ darstellt;
R₁₆ Wasserstoff, C₁-C₁₈-Alkyl, C₃-C₁₈-Alkenyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Tetrahydrofurfuryl, eine Gruppe der Formel (IIIf),

oder C₂-C₄-Alkyl, das in der 2-, 3- oder 4-Stellung mit -OH, C₁-C₈-Alkoxy, Di(C₁-C₄-alkyl)amino oder einer Gruppe der Formel (Ie') substituiert ist, darstellt;
R₁₁ eine der für R₁₆ angegebenen Definitionen aufweist und
die Reste B unabhängig voneinander eine der für A gegebenen Definitionen aufweisen und worin Formel (Ie') und alle anderen Symbole wie vorstehend für Formel Ia definiert sind.Particularly preferred is a compound of formula IIIb

wherein
the radicals A independently represent -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of the formula (IIId);

X represents -O- or> NR ₁₆ ;
R _{16 is} hydrogen, C ₁ -C ₁₈ -alkyl, C ₃ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (IIIf),

or C ₂ -C ₄ -alkyl which is in the 2, 3 or 4 position with -OH, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of the formula ( Ie ') is substituted;
R _{11 has} one of the definitions given for R ₁₆ and
the radicals B independently of one another have one of the definitions given for A and in which formula (Ie ') and all other symbols are as defined above for formula Ia.

worin
R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen, oder R₁ und R₂, zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄, zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen.The radicals B, R ₁₁ and R ₁₂ in the individual repeating units may be the same or different from each other within the meanings indicated. (j ') A compound of the formula (2a)

wherein
R ₁ , R ₂ , R ₃ and R _{4 are} independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ , together with the carbon atom to which they are attached, are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ , together with the carbon atom to which they are attached, represent C ₅ -C ₁₂ -cycloalkyl.

Specific examples of hydrogenated products of the present invention include the following compounds:
1-propoxy-2,2,6,6-tetramethyl-4-piperidone,
1-propoxy-2,2,6,6-tetramethyl-4-piper idol,
Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) (3 ', 5', - di-tert-butyl-4'-hydroxybenzyl) butylmalonate,
Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) succinate,
N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -hexane-1,6-diamine,
N-butyl-1-propoxy-2,2,6,6-tetramethyl-4-piperidinamine,
5- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -2-cycloundecyloxazol,
1,6-hexanediyl-N, N-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidylformamid)
1,5-dioxaspiro (5.5) undecane-3,3-dicarboxylic acid bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) ester,
1,5,8,12-tetrakis (2 ', 4'-bis (1''-propoxy-2'',2'',6'',6''-tetramethyl-4''- piperidyl (butyl) amino) -1 ', 3', 5'-triazin-6'-yl) -1,5,8,12-tetraazadodecane,
1,3,5-tris (N-cyclohexyl-N- (1-propoxy-2,2,6,6-tetramethylpiperazin-3-on-4-yl) amino) -s-triazine,
linear or cyclic condensates of N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
Tris (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
Tetrakis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
1,1 '- (1,2-ethanediyl) -bis- (4-propoxy-3,3,5,5-tetramethylpiperazinone),
4-benzoyl-1-propoxy-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine,
3-n-octyl-8-propoxy-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione,
linear or cyclic condensates of N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine,
the condensate of 2-chloro-4,6-bis (4-n-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3) aminopropylamino) ethane,
8-propoxy-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione,
3-dodecyl-1- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) pyrrolidin-2,5-dione,
a mixture of 4-hexadecyloxy and 4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine,
a condensation product of N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine,
a condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, and 4-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidine;
N- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimid,
2-undecyl-8-propoxy-7,7,9,9-tetramethyl-1-oxa-3,8-di-aza-4-oxo-spiro [4.5] decane,
a reaction product of 8-propoxy-7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane and epichlorohydrin;
N, N'-bis-formyl-N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine,
Poly [methylpropyl-3-oxy-4- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)] siloxane,
the reaction product of maleic anhydride-α-olefin copolymer with 1-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine or the compound
R-NH- (CH ₂ ) ₃ -N (R) - (CH ₂ ) ₂ -N (R) - (CH ₂ ) ₃ -NH-R
R =

The compounds of formulas I, III and V, in particular IIIa and IIIb, can advantageously be used for stabilizing organic material against the damaging effect of light, oxygen and / or heat, in particular for stabilizing synthetic organic polymers or compositions containing these compounds become. They are characterized by high thermal stability, substrate compatibility and good resistance in the substrate.

• 1. Polymere von Monoolefinen und Diolefinen, beispielsweise Polypropylen, Polyisobutylen, Polybut-1-en, Poly-4-methylpent-1-en, Polyisopren oder Polybutadien, sowie Polymere von Cycloolefinen, beispielsweise Cyclopenten oder Norbornen, Polyethylen (das gegebenenfalls vernetzt sein kann), z. B. hochdichtes Polyethylen (HDPE), hochdichtes Polyethylen mit hohem Molekulargewicht (HDPE-HMW), hochdichtes Polyethylen mit sehr hohem Molekulargewicht (HDPE-UHMW), mitteldichtes Polyethylen (HDPE), niederdichtes Polyethylen (LDPE), linear niederdichtes Polyethylen (LLDPE), (VLDPE) und (ULDPE).

Examples of polymers which can be stabilized in this way are the following:

• 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and polymers of cycloolefins, for example cyclopentene or norbornene, polyethylene (which may optionally be crosslinked ), z. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

• a) Radikalische Polymerisation (normalerweise unter Hochdruck und bei erhöhter Temperatur).
• b) Katalytische Polymerisation unter Verwendung eines Katalysators, der normalerweise ein oder mehr als ein Metall der Gruppen IVb, Vb, VIb oder VIII des Periodensystems der Elemente enthält. Diese Metalle haben gewöhnlich einen oder mehr als einen Liganden, im allgemeinen Oxide, Halogenide, Alkoholate, Ester, Ether, Amine, Alkyle, Alkenyle und/oder Aryle, die entweder π- oder σ-koordiniert sein können. Diese Metallkomplexe können in freier Form oder fixiert an Substraten vorliegen, im allgemeinen an aktiviertem Magnesiumchlorid, Titan(III)chlorid, Aluminiumoxid oder Siliciumdioxid. Diese Katalysatoren können in dem Polymerisationsmedium löslich oder unlöslich sein. Die Katalysatoren können selbst bei der Polymerisation verwendet werden oder zusätzliche Aktivatoren können verwendet werden, im allgemeinen Metallalkyle, Metallhydride, Metallalkylhalogenide, Metallalkyloxide oder Metallalkyloxane, wobei die Metalle Elemente der Gruppen Ia, IIa und/oder IIIa des Periodensystems der Elemente sind. Die Aktivatoren können zweckmäßigerweise mit zusätzlichen Ester-, Ether-, Amin- oder Silylethergruppen modifiziert sein. Diese Katalysatorsysteme werden gewöhnlich Phillips-, Standard Oil Indiana-, Ziegler(-Natta)-, TNZ(DuPont)-, Metallocen- oder Einzelaktivstellenkatalysatoren (single site catalysts (SSC)) genannt.

• 2. Gemische von Polymeren, die unter 1) angeführt wurden, zum Beispiel Gemische von Polypropylen mit Polyisobutylen, Polypropylen mit Polyethylen (zum Beispiel PP/HDPE, PP/LDPE) und Gemische von verschiedenen Polyethylenarten (zum Beispiel LDPE/HDPE).
• 3. Copolymere von Monoolefinen und Diolefinen miteinander oder mit anderen Vinylmonomeren, zum Beispiel Ethylen/Propylen-Copolymere, lineares niederdichtes Polyethylen (LLDPE) und dessen Gemische mit niederdichtem Polyethylen (LDPE), Propylen/But-1-en-Copolymere, Propylen/Isobutylen-Copolymere, Ethylen/But-1-en-Copolymere, Ethylen/Hexen-Copolymere, Ethylen/Methylpenten-Copolymere, Ethylen/Hepten-Copolymere, Ethylen/Octen-Copolymere, Propylen/Butadien-Copolymere, Isobutylen/Isopren-Copolymere, Ethylen/Alkylacrylat-Copolymere, Ethylen/Alkylmethacrylat-Copolymere, Ethylen/Vinylacetat-Copolymere und deren Copolymere mit Kohlenmonoxid oder Ethylen/Acrylsäure-Copolymere und deren Salze (Ionomere) sowie Terpolymere von Ethylen mit Propylen und einem Dien, wie Hexadien, Dicyclopentadien oder Ethyliden-Norbornen sowie Gemische von solchen Copolymeren miteinander und mit Polymeren, die in 1) vorstehend angeführt wurden, zum Beispiel Polypropylen/Ethylen-Propylen-Copolymere, LDPE/Ethylen-Vinylacetat-Copolymere (EVA), LDPE/Ethylen-Acrylsäure-Copolymere (EAA), LLDPE/EVA, LLDPE/EAA und alternierende oder statistische Polyalkylen/Kohlenmonoxid-Copolymere und Gemische davon mit anderen Polymeren, z. B. Polyamiden.
• 4. Kohlenwasserstoffharze (zum Beispiel C₅-C₉) einschließlich hydrierten Modifizierungen davon (zum Beispiel Klebrigmacher) und Gemische von Polyalkylenen und Stärke.
• 5. Polystyrol, Poly-(p-methylstyrol), Poly-(α-methylstyrol).
• 6. Copolymere von Styrol oder α-Methylstyrol mit Dienen oder Acrylderivaten, zum Beispiel Styrol/Butadien, Styrol/Acrylnitril, Styrol/Alkylmethacrylat, Styrol/Butadien/Alkylacrylat, Styrol/Butadien/Alkylmethacrylat, Styrol/Maleinsäureanhydrid, Styrol/Acrylnitril/Methylacrylat; Gemische hoher Schlagfestigkeit aus Styrolcopolymeren und anderem Polymer, zum Beispiel Polyacrylat, ein Dienpolymer oder ein Ethylen/Propylen/Dienterpolymer; und Blockcopolymere von Styrol, wie Styrol/Butadien/Styrol, Styrol/Isopren/Styrol, Styrol/Ethylen/Butylen/Styrol oder Styrol/Ethylen/Propylen/Styrol.
• 7. Pfropfcopolymere von Styrol oder α-Methylstyrol, zum Beispiel Styrol auf Polybutadien, Styrol auf Polybutadien-Styrol oder Polybutadien-Acrylnitril-Copolymere; Styrol und Acrylnitril (oder Methacrylnitril) auf Polybutadien; Styrol, Acrylnitril und Methylmethacrylat auf Polybutadien; Styrol und Maleinsäureanhydrid auf Polybutadien; Styrol, Acrylnitril und Maleinsäureanhydrid oder Maleimid auf Polybutadien; Styrol und Maleimid auf Polybutadien; Styrol und Alkylacrylate oder -methacrylate auf Polybutadien; Styrol und Acrylnitril auf Ethylen/Propylen/Dien-Terpolymeren; Styrol und Acrylnitril auf Polyalkylacrylaten oder Polyalkylmethacrylaten, Styrol und Acrylnitril auf Acrylat/Butadien-Copolymeren sowie Gemische davon mit den unter 6) aufgeführten Copolymeren, zum Beispiel die Copolymergemische, bekannt als ABS-, MBS-, ASA- oder AES-Polymere.
• 8. Halogenhaltige Polymere, wie Polychloropren, chlorierte Kautschuke, chloriertes und bromiertes Copolymer aus Isobutylen-Isopren (Halogenbutylkautschuk), chloriertes oder sulfochloriertes Polyethylen, Copolymere von Ethylen und chloriertem Ethylen, Epichlorhydrin-Homo- und -Copolymere, insbesondere Polymere aus halogenhaltigen Vinylverbindungen, zum Beispiel Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylfluorid, Polyvinylidenfluorid sowie Copolymere davon, wie Vinylchlorid/Vinylidenchlorid-, Vinylchlorid/Vinylacetat- oder Vinylidenchlorid/Vinylacetat-Copolymere.
• 9. Polymere, die abgeleitet sind von α,β-ungesättigten Säuren und Derivaten davon, wie Polyacrylate und Polymethacrylate, Polymethylmethacrylate, Polyacrylamide und Polyacrylnitrile, schlagzäh modifiziert mit Butylacrylat.
• 10. Copolymere von Monomeren, die unter 9) aufgeführt wurden, miteinander oder mit anderen ungesättigten Monomeren, zum Beispiel Acrylnitril/Butadien-Copolymere, Acrylnitril/Alkylacrylat-Copolymere, Acrylnitril/Alkoxyalkylacrylat- oder Acrylnitril/Vinylhalogenid-Copolymere oder Acrylnitril/Alkylmethacrylat/Butadien-Terpolymere.
• 11. Polymere, die von ungesättigten Alkoholen und Aminen abgeleitet sind, oder Acylderivate oder Acetale davon, zum Beispiel Polyvinylalkohol, Polyvinylacetat, Polyvinylstearat, Polyvinylbenzoat, Polyvinylmaleat, Polyvinylbutyral, Polyallylphthalat oder Polyallylmelamin sowie deren Copolymere mit Olefinen, die unter 1) vorstehend erwähnt wurden.
• 12. Homopolymere und Copolymere von cyclischen Ethern, wie Polyalkylenglycole, Polyethylenoxid, Polypropylenoxid oder Copolymere davon mit Bisglycidylethern.
• 13. Polyacetale, wie Polyoxymethylen und jene Polyoxymethylene, die Ethylenoxid als Comonomer enthalten, Polyacetale, modifiziert mit thermoplastischen Polyurethanen, Acrylaten oder MBS.
• 14. Polyphenylenoxide und -sulfide und Gemische von Polyphenylenoxiden mit Styrolpolymeren oder Polyamiden.
• 15. Polyurethane, die einerseits von Polyethern, Polyestern oder Polybutadienen mit endständigen Hydroxylgruppen und andererseits von aliphatischen oder aromatischen Polyisocyanaten sowie Vorstufen davon abgeleitet sind.
• 16. Polyamide und Copolyamide, die abgeleitet sind von Diaminen und Dicarbonsäuren und/oder von Aminocarbonsäuren oder den entsprechenden Lactamen, wie Polyamid 4, Polyamid 6, Polyamid 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, Polyamid 11, Polyamid 12, aromatische Polyamide, ausgehend von m-Xyloldiamin und Adipinsäure; Polyamide, hergestellt aus Hexamethylendiamin und Isophthalsäure oder/und Terephthalsäure und gegebenenfalls mit einem Elastomer als Modifizierungsmittel, zum Beispiel Poly-2,4,4-trimethylhexamethylenterephthalamid oder Poly-m-phenylenisophthalamid und ebenfalls Blockcopolymere der vorstehend angeführten Polyamide mit Polyolefinen, Olefin-Copolymeren, Ionomeren oder chemisch gebundenen oder gepfropften Elastomeren; oder mit Polyethern, zum Beispiel mit Polyethylenglycol, Polypropylenglycol oder Polytetramethylenglycol; sowie Polyamide oder Copolyamide, modifiziert mit EPDM oder ABS; und Polyamide, kondensiert während der Herstellung (RIM-Polyamid-Systeme).
• 17. Polyharnstoffe, Polyimide und Polyamid-Imide, Polyetherimide, Polyesterimide, Polyhydantoine und Polybenzimidazole.
• 18. Polyester, die abgeleitet sind von Dicarbonsäuren und Diolen und/oder von Hydroxycarbonsäuren oder den entsprechenden Lactonen, zum Beispiel Polyethylenterephthalat, Polybutylenterephthalat, Poly-1,4-dimethylolcyclohexanterephthalat und Polyhydroxybenzoate sowie Block-Copolyether-Ester, abgeleitet von Polyethern mit Hydroxylendgruppen und auch Polyester, modifiziert mit Polycarbonaten oder MBS.
• 19. Polycarbonate und Polyestercarbonate.
• 20. Polysulfone, Polyethersulfone und Polyetherketone.
• 21. Vernetzte Polymere, abgeleitet von Aldehyden einerseits und Phenolen, Harnstoffen und Melaminen andererseits, wie Phenol/Formaldehydharze, Harnstoff/Formaldehydharze und Melamin/Formaldehydharze.
• 22. Trocknende und nichttrocknende Alkydharze.
• 23. Ungesättigte Polyesterharze, abgeleitet von Copolyestern gesättigter und ungesättigter Dicarbonsäuren mit mehrwertigen Alkoholen und Vinylverbindungen als Vernetzungsmittel und auch halogenhaltige Modifizierungen davon niederer Entflammbarkeit.
• 24. Vernetzbare Acrylharze, abgeleitet von substituierten Acrylaten, zum Beispiel Epoxyacrylaten, Urethanacrylaten oder Polyesteracrylaten.
• 25. Alkydharze, Polyesterharze oder Acrylatharze, vernetzt mit Melaminharzen, Harnstoffharzen, Isocyanaten, Isocyanuraten, Polyisocyanaten oder Epoxidharzen.
• 26. Vernetzte Epoxidharze, abgeleitet von aliphatischen, cycloaliphatischen, heterocyclischen oder aromatischen Glycidylverbindungen, z. B. Produkte von Diglycidylethern von Bisphenol A und Bisphenol F, die mit gebräuchlichen Härtern, wie Anhydriden oder Aminen, vernetzt sind, gegebenenfalls mit Beschleunigern.
• 27. Gemische von Polymeren, die vorstehend genannt wurden (Polyblends), zum Beispiel PP/EPDM, Polyamid/EPDM oder ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/thermoplastisches PUR, PC/thermoplastisches PUR, POM/Acrylat, POM/MBS, PPO/HIPS, PPO/PA 6,6 und Copolymere, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS oder PBT/PET/PC.

Polyolefins, ie polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, in particular by the following methods:

• a) Radical polymerization (usually under high pressure and at elevated temperature).
• b) Catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table of the Elements. These metals usually have one or more than one ligand, generally oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be either π- or σ-coordinated. These metal complexes may be in free form or fixed to substrates, generally on activated magnesium chloride, titanium (III) chloride, alumina or silica. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts themselves may be used in the polymerization or additional activators may be used, generally metal alkyls, metal hydrides, metal alkyl halides, metal alkyloxides or metal alkyloxanes, the metals being elements of groups Ia, IIa and / or IIIa of the Periodic Table of the Elements. The activators may conveniently be modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are commonly called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSCs).

• 2. Mixtures of 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 its blends with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene Copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / Alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene Norbornene and mixtures of such copolymers with each other and with polymers recited in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyla cetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and blends thereof with other polymers, e.g. B. polyamides.
• 4. Hydrocarbon resins (for example C ₅ -C ₉ ) including hydrogenated modifications thereof (for example tackifiers) and mixtures of polyalkylenes and starch.
• 5. polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).
• 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; High impact strength blends of styrenic copolymers and other polymer, for example polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.
• 7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene terpolymers; Styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers and mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
• 8. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, for Example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.
• 9. Polymers which are derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
• 10. Copolymers of monomers listed under 9) with each other or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, Acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.
• 11. Polymers derived from unsaturated alcohols and amines, or acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine and their copolymers with olefins mentioned under 1) above.
• 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
• 13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• 14. Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene polymers or polyamides.
• 15. Polyurethanes which are derived on the one hand from polyethers, polyesters or polybutadienes with terminal hydroxyl groups and on the other hand from aliphatic or aromatic polyisocyanates and precursors thereof.
• 16. polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as 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-xylenediamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally with an elastomer as modifier, for example poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide and also block copolymers of the abovementioned 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; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during production (RIM polyamide systems).
• 17. Polyureas, polyimides and polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
• 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from polyethers having hydroxyl end groups and also Polyester modified with polycarbonates or MBS.
• 19. polycarbonates and polyestercarbonates.
• 20. polysulfones, polyethersulfones and polyetherketones.
• 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
• 22. Drying and non-drying alkyd resins.
• 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and also halogen-containing modifications thereof of low flammability.
• 24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
• 25. Alkyd resins, polyester resins or acrylate resins, crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
• 26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. B. Products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with conventional hardeners, such as anhydrides or amines, optionally with accelerators.
• 27. Mixtures of polymers mentioned above (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 / Acrylate, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6,6 and Copolymers, PA / HDPE, PA / PP , PA / PPO, PBT / PC / ABS or PBT / PET / PC.

Of particular interest is the use of the compounds of formula IIIa as stabilizers in synthetic organic polymers, for example a coating or bulk polymer or an article formed therefrom, in particular in thermoplastic polymers and corresponding compositions and in coating compositions. Thermoplastic polymers of particular importance in the present compositions are polyolefins and their copolymers, as noted under 1-3 above, thermoplastic polyolefin (TPO), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), polycarbonate as recited in item 19 above and mixtures as recited in Item 27 above. Of particular importance are polyethylene (PE), polypropylene (PP), polycarbonate (PC) and polycarbonate blends, such as PC / ABS blends, as well as acid or metal catalyzed coating compositions.

In general, the compounds according to the invention are added to the material to be stabilized in amounts of from 0.1 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% (based on the material to be stabilized). Particularly preferred is the use of the new compounds in amounts of 0.05 to 1.5%, in particular 0.1 to 0.5%. When compounds of the present invention are used as a flame retardant, dosages are usually higher, for example, 0.1 to 25 percent by weight, mainly 0.1 to 10 percent by weight, of the organic material to be stabilized and to be flame-retarded.

Incorporation into the materials can be accomplished, for example, by admixing or coating the compounds of Formula I, IIIa, IV, V and, if desired, other additives by the methods commonly employed in the art. When polymers, especially synthetic polymers, are included, incorporation may occur before or during the molding process or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latexes. A further possibility for incorporating the compounds of the formula IIIa into polymers is to add them to the corresponding monomers or before crosslinking before, during or directly after the polymerization. In this connection, the compound of the formula IIIa may be added as it is or else in encapsulated form (for example in waxes, oils or polymers). In the case of addition before or during the polymerization, the compounds of formula IIIa may also act as chain-length controlling agents of the polymers (chain-terminating agents).

The compounds of formula IIIa can also be added in the form of a masterbatch containing the compound in a concentration of, for example, 2.5 to 25% by weight of the polymers to be stabilized.

• – als Emulsion oder Dispersion (beispielsweise zu Latizes oder Emulsionspolymeren),
• – als Trockengemisch während des Anmischens der weiteren Komponenten oder Polymergemische,
• – durch direkte Einführung in die Verarbeitungsanlage (beispielsweise Extruder, Innenmischer, usw.),
• – als Lösung oder Schmelze.

The compounds of formula IIIa may be conveniently incorporated by the following methods:

• As emulsion or dispersion (for example to latices or emulsion polymers),
• As a dry mixture during the mixing of the further components or polymer mixtures,
• - by direct introduction into the processing plant (eg extruders, internal mixers, etc.),
• - as a solution or melt.

The novel polymer compositions can be used in various forms and / or processed into various products, for example (to give) films, fibers, tapes, molding compounds, profiles or as binders for coating materials, adhesives or putties.

• 1. Antioxidantien
• 1.1. Alkylierte Monophenole, zum Beispiel 2,6-Di-tert.-butyl-4-methylphenol, 2-tert.-Butyl-4,6-dimethylphenol, 2,6-Di-tert.-butyl-4-ethylphenol, 2,6-Di-tert.-butyl-4-n-butylphenol, 2,6-Di-tert.-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methylphenol, 2-(α-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert.-butyl-4-methoxymethylphenol, Nonylphenole, die in den Seitenketten linear oder verzweigt sind, zum Beispiel 2,6-Dinonyl-4-methylphenol, 2,4-Dimethyl-6-(1'-methylundec-1'-yl)-phenol, 2,4-Dimethyl-6-(1'-methylheptadec-1'-yl)-phenol, 2,4-Dimethyl-6-(1'-methyltridec-1'-yl)-phenol und Gemische davon.
• 1.2. Alkylthiomethylphenole, zum Beispiel 2,4-Dioctylthiomethyl-6-tert.-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethyiphenol, 2,6-Didodecylthiomethyl-4-nonylphenol.
• 1.3. Hydrochinone und alkylierte Hydrochinone, zum Beispiel 2,6-Di-tert.-butyl-4-methoxyphenol, 2,5-Di-tert.-butylhydrochinon, 2,5-Di-tert.-amylhydrochinon, 2,6-Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert.-butylhydrochinon, 2,5-Di-tert.-butyl-4-hydroxyanisol, 3,5-Di-tert.-butyl-4-hydroxyanisol, 3,5-Di-tert.-butyl-4-hydroxyphenylstearat, Bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)adipat.
• 1.4. Tocopherole, zum Beispiel α-Tocopherol, β-Tocopherol, γ-Tocopherol, δ-Tocopherol und Gemische davon (Vitamin E).
• 1.5. Hydroxylierte Thiodiphenylether, zum Beispiel 2,2'-Thiobis(6-tert.-butyl-4-methylphenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert.-butyl-3-methylphenol), 4,4'-Thiobis(6-tert.-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-sec.-amylphenol), 4,4'-Bis-(2,6-dimethyl-4-hydroxyphenyl)disulfid.
• 1.6. Alkylidenbisphenole, zum Beispiel 2,2'-Methylenbis(6-tert.-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert.-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-Methyleqnbis(4-methyl-6-cyclohexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert.-butylphenol), 2,2'-Ethylidenbis(4,6-di-tert.-butylphenol), 2,2'-Ethylidenbis(6-tert.-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenbis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenbis(2,6-di-tert.-butylphenol), 4,4'-Methylenbis(6-tert.-butyl-2-methylphenol), 1,1-Bis(5-tert.-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert.-butyl-4-hydroxy-2-methylphenyl)butan, 1,1-Bis(5-tert.-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)butyrat], Bis(3-tert.-butyl-4-hydroxy-5-methylphenyl)dicyclopentadien, Bis[2-(3'-tert.-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert.-butyl-4-methylphenyl]-terephthalat, 1,1-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5,5-Tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)pentan.
• 1.7. O-, N- und S-Benzylverbindungen, zum Beispiel 3,5,3',5'-Tetra-tert.-butyl-4,4'-dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetat, Tridecyl-4-hydroxy-3,5-di-tert.-butylbenzylmercaptoacetat, Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amin, Bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalat, Bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-sulfid, Isooctyl-3,5-di-tert.-butyl-4-hydroxybenzylmercaptoacetat.
• 1.8. Hydroxybenzylierte Malonate, zum Beispiel Dioctadecyl-2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonat, Dioctadecyl-2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonat, Didodecylmercaptoethyl-2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)malonat, Bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)malonat.
• 1.9. Aromatische Hydroxybenzylverbindungen, zum Beispiel 1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-Bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)phenol.
• 1.10. Triazinverbindungen, zum Beispiel 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-1,3,5-triazin, 2,4,6-Tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-1,2,3-triazin, 1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-Tris-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-1,3,5-triazin, 1,3,5-Tris-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazin, 1,3,5-Tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurat.
• 1.11. Benzylphosphonate, zum Beispiel Dimethyl-2,5-di-tert.-butyl-4-hydroxybenzylphosphonat, Diethyl-3,5-di-tert.-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-3,5-di-tert.-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonat, das Calciumsalz des 3,5-Di-tert.-butyl-4-hydroxybenzylphosphonsäuremonoethylesters.
• 1.12. Acylaminophenole, zum Beispiel Laurinsäure-4-hydroxyanilid, Stearinsäure-4-hydroxyanilid, Octyl-N-(3,5-di-tert.-butyl-4-hydroxyphenyl)-carbamat.
• 1.13. Ester von 1-(3,5-Di-tert.-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, beispielsweise mit Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythrit, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octan.
• 1.14. Ester von β-(5-tert.-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, beispielsweise mit Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythrit, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octan.
• 1.15. Ester von β-(3,5-Dicyclohexyl-4-hydroxyphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen, beispielsweise mit Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythrit, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octan.
• 1.16. Ester von 3,5-Di-tert.-butyl-4-hydroxyphenylessigsäure mit ein- oder mehrwertigen Alkoholen, beispielsweise mit Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythrit, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octan.
• 1.17. Amide von β-(3,5-Di-tert.-butyl-4-hydroxphenyl)propionsäure, beispielsweise N,N'-Bis(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)trimethylendiamid, N,N'-Bis(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)-hydrazid, N,N'-Bis[2-(3-[3,5-di-tert.-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamid (Naugard^®XL-1, vertrieben von Uniroyal).
• 1.18. Ascorbinsäure (Vitamin C)
• 1.19. Amin-Antioxidantien, zum Beispiel N,N'-Diisopropyl-p-phenylendiamin, N,N'-Di-sec.-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Di-methylbutyl)-N'-phenyl-p-phenylendiamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p-Toluolsulfamoyl)-diphenylamin, N,N'-Dimethyl-N,N'-di-sec.-butyl-p-phenylendiamin, Diphenylamin, N-Allyldiphenylamin, 4-Isopropoxydiphenylamin, N-Phenyl-1-naphthylamin, N-(4-tert.-Octylphenyl)-1-naphthylamin, N-Phenyl-2-naphthylamin, octyliertes Diphenylamin, z. B. p,p'-Di-tert.-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4-Dodecanoylaminophenol, 4-Octadecanoylaminophenol, Bis(4-methoxyphenyl)amin, 2,6-Di-tert.-butyl-4-dimethylaminomethylphenol, 2,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetramethyl-4,4'-diaminodiphenylmethan, 1,2-Bis[(2-methylphenyl)amino]ethan, 1,2-Bis(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(1',3'-dimethylbutyl)phenyl]amin, tert.-octyliertes N-Phenyl-1-naphthylamin, ein Gemisch von mono- und dialkylierten tert.-Butyl/tert.-Octyldiphenylaminen, ein Gemisch von mono- und di-alkylierten Nonyldiphenylaminen, ein Gemisch von mono- und dialkylierten Dodecyldiphenylaminen, ein Gemisch von mono- und dialkylierten Isopropyl/Isohexyldiphenylaminen, ein Gemisch von mono- und dialkylierten tert.-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothiazin, Phenothiazin, ein Gemisch von mono- und dialkylierten tert.-Butyl/tert.-Octylphenothiazinen, ein Gemisch von mono- und dialkylierten tert.-Octylphenothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4-diaminobut-2-en, N,N-Bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylendiamin, Bis(2,2,6,6-tetramethylpiperid-4-yl)sebacat, 2,2,6,6-Tetramethylpiperidin-4-on, 2,2,6,6-Tetramethylpiperidin-4-ol.
• 2. UV-Absorptionsmittel und Lichtstabilisatoren
• 2.1. 2-(2'-Hydroxyphenyl)benzotriazole, zum Beispiel 2-(2'-Hydroxy-5'-methylphenyl)benzotriazol, 2-(3',5'-Di-tert.-butyl-2'-hydroxyphenyl)benzotriazol, 2-(5'-tert.-Butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-Hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert.-butyl-2'-hydroxyphenyl)-5-chlorbenzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-methylphenyl)-5-chlorbenzotriazol, 2-(3'-sec.-Butyl-5'-tert.-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di-tert.-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3'‚5,-Bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorbenzotriazol, 2-(3'-tert.-Butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlorbenzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorbenzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert.-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3'-tert.-Butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'-Methylenbis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das Umesterungsprodukt von 2-[3'-tert.-Butyl-5'-(2-methoxycarbonylethyl-2'-hydroxyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R-CH₂CH₂-COO-CH₂CH₂]₂-, wobei R = 3'-tert.-Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-Hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazol; 2-(2'-Hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazol.
• 2.2. 2-Hydroxybenzophenone, zum Beispiel die 4-Hydroxy-, 4-Methoxy-, 4-Octyloxy-, 4-Decyloxy-, 4-Dodecyloxy-, 4-Benzyloxy-, 4,2',4'-Trihydroxy- und 2'-Hydroxy-4,4'-dimethoxyderivate.
• 2.3. Ester von substituierten und unsubstituierten Benzoesäuren, wie zum Beispiel Salicylsäure-4-tert.-butylphenylester, Salicylsäurephenylester, Salicylsäureoctylphenylester, Dibenzoylresorcin, Bis-(4-tert.-butylbenzoyl)-resorcin, Benzoylresorcin, 3,5-Di-tert.-butyl-4-hydroxybenzoesäure-2,4-di-tert.-butylphenylester, 3,5-Di-tert.-butyl-4-hydroxybenzoesäurehexadecylester, 3,5-Di-tert.-butyl-4-hydroxybenzoesäureoctadecylester, 3,5-Di-tert.-butyl-4-hydroxybenzoesäure-2-methyl-4,6-di-tert.-butylphenylester.
• 2.4. Acrylate, zum Beispiel α,-Cyano-β,β-diphenylacrylsäureethylester, α-Cyano-β,β-diphenylacrylsäureisooctylester, α-Carbomethoxyzimtsäuremethylester, α-Cyano-β-methyl-p-methoxyzimtsäuremethylester, α-Cyano-β-methyl-p-methoxyzimtsäurebutylester, α-Carbomethoxy-p-methoxyzimtsäuremethylester und N-(β-Carbomethoxy-β-cyanovinyl)-2-methylindolin.
• 2.5. Nickelverbindungen, zum Beispiel Nickelkomplexe von 2,2'-Thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], wie der 1:1- oder 1:2-Komplex, mit oder ohne zusätzliche Liganden, wie n-Butylamin, Triethanolamin oder N-Cyclohexyldiethanolamin, Nickeldibutyldithiocarbamat, Nickelsalze von Monoalkylestern, beispielsweise dem Methyl- oder Ethylester, von 4-Hydroxy-3,5-di-tert.-butylbenzylphosphonsäure, Nickelkomplexe von Ketoximen, beispielsweise von 2-Hydroxy-4-methylphenylundecylketoxim, Nickelkomplexe von 1-Phenyl-4-lauroyl-5-hydroxypyrazol mit oder ohne zusätzliche Liganden.
• 2.6. Sterisch gehinderte Amine, zum Beispiel Bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacat, Bis(2,2,6,6-tetramethyl-4-piperidyl)succinat, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacat, Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacat, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert.-butyl-4-hydroxybenzylmalonat, das Kondensat von 1-(2-Hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidin und Bernsteinsäure, lineare oder cyclische Kondensate von N,N'-Bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylendiamin und 4-tert.-Octylamino-2,6-dichlor-1,3,5-triazin, Tris-(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetat, Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butantetracarboxylat, 1,1'-(1,2-Ethandiyl)bis-(3,3,5,5-tetramethylpiperazinon), 4-Benzoyl-2,2,6,6-tetramethylpiperidin, 4-Stearyloxy-2,2,6,6-tetramethylpiperidin, Bis-(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert.-butylbenzyl)malonat, 3-n-Octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-[4.5]-decan-2,4-dion, Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacat, Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinat, lineare oder cyclische Kondensate von N,N'-Bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamin und 4-Morpholino-2,6-dichlor-1,3,5-triazin, das Kondensat von 2-Chlor-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazin und 1,2-Bis-(3-aminopropylamino)ethan, das Kondensat von 2-Chlor-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazin und 1,2-Bis-(3-aminopropyl-amino)ethan, 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decan-2,4-dion, 3-Dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dion, 3-Dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidin-2,5-dion, ein Gemisch von 4-Hexadecyloxy- und 4-Stearyloxy-2,2,6,6-tetramethylpiperidin, ein Kondensationsprodukt von N,N'-Bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamin und 4-Cyclohexylamino-2,6-dichlor-1,3,5-triazin, ein Kondensationsprodukt von 1,2-Bis(3-aminopropylamino)ethan und 2,4,6-Trichlor-1,3,5-triazin sowie 4-Butylamino-2,2,6,6-tetramethylpiperidin (CAS-Reg.-Nr. [136504-96-6]); N-(2,2,6,6-Tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1,2,2,6,6-Pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-Undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decan, ein Reaktionsprodukt von 7,7,9,9-Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decan und Epichlorhydrin, 1,1-Bis-(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethen, N,N'-Bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamin, Diester von 4-Methoxymethylenmalonsäure mit 1,2,2,6,6-Pentamethyl-4-hydroxypiperidin, Poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxan, Reaktionsprodukt von Maleinsäureanhydrid-α-Olefin-Copolymer mit 2,2,6,6-Tetramethyl-4-aminopiperidin oder 1,2,2,6,6-Pentamethyl-4-aminopiperidin, 2,4-Bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazin.
• 2.7. Oxamide, zum Beispiel 4,4'-Dioctyloxyoxanilid, 2,2'-Diethoxyoxanilid, 2,2'-Dioctyloxy-5,5'-di-tert.-butoxanilid, 2,2'-Didodecyloxy-5,5'-di-tert.-butoxanilid, 2-Ethoxy-2'-ethyloxanilid, N,N'-Bis(3-dimethylaminopropyl)oxamid, 2-Ethoxy-5-tert.-butyl-2'-ethoxanilid und dessen Gemisch mit 2-Ethoxy-2'-ethyl-5,4'-di-tert.-butoxanilid, Gemische von o- und p-Methoxy-disubstituierten Oxaniliden und Gemische von o- und p-Ethoxy-disubstituierten Oxaniliden.
• 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazine, zum Beispiel 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[4-(Dodecyloxy/Tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazin, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazin, 2-{2-Hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy)-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-{2-Hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazin, worin die Octyleinheit ein Gemisch verschiedener Isomere ist.
• 3. Metalldesaktivatoren, zum Beispiel N,N'-Diphenyloxamid, N-Salicylal-N'-salicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)hydrazin, 3-Salicyloylamino-1,2,4-triazol, Bis(benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Sebacoyl-bisphenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyloyl)oxalyldihydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid.
• 4. Phosphite und Phosphonite, zum Beispiel Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tris(nonylphenyl)phosphit, Trilaurylphosphit, Trioctadecylphosphit, Distearylpentaerythritdiphosphit, Tris(2,4-di-tert.-butylphenyl)phosphit, Diisodecylpentaerythritdiphosphit, Bis-(2,4-di-tert.-butylphenyl)pentaerythritdiphosphit, Bis-(2,6-di-tert.-butyl-4-methylphenyl)pentaerythritdiphosphit, Diisodecyloxypentaerythritdiphosphit, Bis-(2,4-di-tert.-butyl-6-methylphenyl)pentaerythritdiphosphit, Bis-(2,4,6-tris-tert.-butylphenyl)pentaerythrjtdiphosphit, Tristearylsorbittriphosphit, Tetrakis(2,4-di-tert.-butylphenyl)-4,4'-biphenylendiphosphonit, 6-Isooctyloxy-2,4,8,10-tetra-tert.-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-Fluor-2,4,8,10-tetra-tert.-butyl-12-methyldibenz[d,g]-1,3,2-dioxaphosphocin, Bis-(2,4-di-tert.-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert.-butyl-6-methylphenyl)ethylphosphit, 2,2',2''-Nitrilo[triethyltris(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphit.

In addition to the compounds of formula IIIa, the novel compositions may comprise as further component C one or more conventional additives, such as those identified below.

• 1. Antioxidants
• 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4, 6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-Dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl ) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol and mixtures thereof.
• 1.2. Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
• 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
• 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
• 1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl) 3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.
• 1.6. Alkylidene bisphenols, for example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4 -methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylsilbenz (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- Methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol ), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2 -methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy) 2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert. -butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, B Is [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl 2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2 -methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
• 1.7. O, N and S benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy) 2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5- methylbenzyl) malonate, didodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2 , malonate 2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl).
• 1.9. Aromatic hydroxybenzyl compounds, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di tert -butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
• 1.10. Triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis ( 3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4, 6-Tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
• 11.1. Benzyl phosphonates, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl 4-Hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonsäuremonoethylesters.
• 1.12. Acylaminophenols, for example, lauric acid 4-hydroxyanilide, stearic acid 4-hydroxyanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
• 1.13. Esters of 1- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2 , 6,7-trioxabicyclo [2.2.2] octane.
• 1.14. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol , Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 1.15. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo [2.2.2] octane.
• 16.1. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2 Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphate 2,6,7-trioxabicyclo [2.2.2] octane.
• 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N ' bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ^® XL-1, supplied by Uniroyal).
• 1.18. Ascorbic acid (vitamin C)
• 19.1. Amine antioxidants, for example N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) - N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N , N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) 1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. B. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di- tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2 -methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1 -naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and di-alkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines , a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert. Octylphenothiazines, a mixture of n mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6- tetramethylpiperid-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidine 4-ol.
• 2. UV absorbers and light stabilizers
• 2.1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3 'sec -butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert. -amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5, bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-butyl) hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole; 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5 chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxybenzoyl) 5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2 octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'- hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl-2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ ] ₂ -, wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl, 2- [2'-hydroxy-3 '- (α, α-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- (2'-Hydroxy-3' - (1,1,3,3-tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.
• 2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'hydroxy-4,4'-dimethoxy derivatives.
• 2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl 4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5- di-tert-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-tert-butylphenyl ester.
• 2.4. Acrylates, for example α, cyano-β, β-diphenylacrylate, ethyl α-cyano-β, β-diphenylacrylate, α-carbomethoxycinnamate, α-cyano-β-methyl-p-methoxycinnamate, α-cyano-β-methyl-p methyl methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.
• 2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, for example the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.
• 2.6. Sterically hindered amines, for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (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-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid , linear or cyclic condensates of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5- triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1 , 1 '- (1,2-ethanediyl) bis- (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-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 -7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4 -dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensates of N, N'-bis - (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis (4 -n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl -7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] -decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl ) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy and 4- Stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 , 3,5-triazine, a condensation product of 1,2-bis (3-aminopr opylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl 7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa 3,8-diaza-4-oxospiro [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-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl- 4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride-α-olefin copolymer with 2,2,6,6- Tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) - N-butylamino] -6- (2-hydroxyethyl) amino-1,3,5-triazine.
• 2.7. Oxamides, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy -2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
• 2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy 3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4 -dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4- methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine , 2- (2-Hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) 2-hydroxypropyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- {2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6 bis (4-phenylphenyl) -1,3,5-triazine, wherein the octyl moiety is a mixture of different isomers.
• 3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl 4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyl adipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
• 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) phosphite. di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocine, 6 Fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6 -methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert .-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2 , 2'-diyl) phosphite.

• 5. Hydroxylamine, zum Beispiel N,N-Dibenzylhydroxylamin, N,N-Diethylhydroxylamin, N,N-Dioctylhydroxylamin, N,N-Dilaurylhydroxylamin, N,N-Ditetradecylhydroxylamin, N,N-Dihexadecylhydroxylamin, N,N-Dioctadecylhydroxylamin, N-Hexadecyl-N-octadecylhydroxylamin, N-Heptadecyl-N-octadecylhydroxylamin, N,N-Dialkylhydroxylamin, abgeleitet von hydriertem Talgamin.
• 6. Nitrone, zum Beispiel, N-Benzyl-α-phenylnitron, N-Ethyl-α-methylnitron, N-Octyl-α-heptylnitron, N-Lauryl-α-undecylnitron, N-Tetradecyl-α-tridecylnitron, N-Hexadecyl-α-pentadecylnitron, N-Octadecyl-α-heptadecylnitron, N-Hexadecyl-α-heptadecylnitron, N-Octadecyl-α-pentadecylnitron, N-Heptadecyl-α-heptadecylnitron, N-Octadecyl-α-hexadecylnitron, Nitron, abgeleitet von N,N-Dialkylhydroxylamin, abgeleitet von hydriertem Talgamin.
• 7. Thiosynergisten, zum Beispiel, Dilaurylthiodipropionat oder Distearylthiodipropionat.
• 8. Peroxidfänger, zum Beispiel Ester von β-Thiodipropionsäure, zum Beispiel die Lauryl-, Stearyl-, Myristyl- oder Tridecylester, Mercaptobenzimidazol oder das Zinksalz von 2-Mercaptobenzimidazol, Zinkdibutyldithiocarbamat, Dioctadecyldisulfid, Pentaerythrittetrakis(β-dodecylmercapto)propionat.
• 9. Polyamidstabilisatoren, zum Beispiel Kupfersalze in Kombination mit Jodiden und/oder Phosphorverbindungen und Salze von zweiwertigem Mangan.
• 10. Basische Costabilisatoren, zum Beispiel, Melamin, Polyvinylpyrrolidon, Dicyandiamid, Triallylcyanurat, Harnstoffderivate, Hydrazinderivate, Amine, Polyamide, Polyurethane, Alkalimetallsalze und Erdalkalimetallsalze von höheren Fettsäuren, zum Beispiel Calciumstearat, Zinkstearat, Magnesiumbehenat, Magnesiumstearat, Natriumricinoleat und Kaliumpalmitat, Antimonbrenzcatechinat oder Zinkbrenzcatechinat.
• 11. Kernbildungsmittel, zum Beispiel anorganische Stoffe, wie Talkum, Metalloxide, wie Titandioxid oder Magnesiumoxid, Phosphate, Carbonate oder Sulfate von, vorzugsweise Erdalkalimetallen; organische Verbindungen, wie Mono- oder Polycarbonsäuren und deren Salze, z. B. 4-tert.-Butylbenzoesäure, Adipinsäure, Diphenylessigsäure, Natriumsuccinat oder Natriumbenzoat; polymere Verbindungen, wie ionische Copolymere (”Ionomere”).
• 12. Füllstoffe und Verstärkungsmittel, zum Beispiel Calciumcarbonat, Silicate, Glasfasern, Glaskugeln, Asbest, Talkum, Kaolin, Glimmer, Bariumsulfat, Metalloxide und -hydroxide, Ruß, Graphit, Holzmehl und Mehle oder Fasern von anderen Naturprodukten, synthetische Fasern.
• 13. Andere Additive, zum Beispiel Weichmacher oder Plastifizierungsmittel, Schmiermittel, Emulgatoren, Pigmente, Rheologieadditive, Katalysatoren, Fließregelungsmittel, optische Aufheller, Flammschutzmittel, antistatische Mittel und Treibmittel.
• 14. Benzofuranone und Indolinone, zum Beispiel jene offenbart in US-A-4 325 863 , US-A-4 338 244 , US-A-5 175 312 , US-A-5 216 052 , US-A-5 252 643 , DE-A-43 16 611 , DE-A-43 16 622 , DE-A-43 16 876 , EP-A-0 589 839 oder EP-A-0 591 102 oder 3-[4-(2-Acetoxyethoxy)phenyl]-5,7-di-tert.-butylbenzofuran-2-on, 5,7-Di-tert.-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-on, 3,3'-Bis[5,7-di-tert.-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-on), 5,7-Di-tert.-butyl-3-(4-ethoxyphenyl)benzofuran-2-on, 3-(4-Acetoxy-3,5-dimethylphenyl)-5,7-di-tert.-butylbenzofuran-2-on, 3-(3,5-Dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert.-butylbenzofuran-2-on, 3-(3,4-Dimethylphenyl)-5,7-di-tert.-butylbenzofuran-2-on, 3-(2,3-Dimethylphenyl)-5,7-di-tert.-butylbenzofuran-2-on.

Particularly preferred are the following phosphites: Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ^® 168, Ciba-Geigy), tris (nonylphenyl) phosphite.

• 5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N- Hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.
• 6. Nitrone, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl -α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, nitrone, derived from N , N-dialkylhydroxylamine derived from hydrogenated tallow amine.
• 7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
• 8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.
• 9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
• 10. Basic costabilizers, for example, melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony catecholate or zinc catechinate ,
• 11. nucleating agents, for example inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and their salts, for. For example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers ("ionomers").
• 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• 13. Other additives, for example plasticizers or plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.
• 14. Benzofuranones and indolinones, for example those disclosed in U.S.-A-4,325,863 . US-A-4,338,244 . US-A-5 175 312 . US-A-5,216,052 . US-A-5,252,643 . DE-A-43 16 611 . DE-A-43 16 622 . DE-A-43 16 876 . EP-A-0 589 839 or EP-A-0 591 102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxy-ethoxy] -phenyl) -benzofuran-2-one), 5,7-di tert -butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3 (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one on, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

The usual additives are expediently used in amounts of 0.1 to 10 wt .-%, for example 0.2-5 wt .-%, based on the material to be stabilized.

worin G Wasserstoff oder Methyl, insbesondere Wasserstoff, enthält, abgeleitet sind; Beispiele von Tetraalkylpiperidinderivaten, die als Costabilisatoren mit erfindungsgemäßen Gemischen verwendet werden können, werden in EP-A-356 677 , Seiten 3–17, Abschnitte a) bis f), angegeben. Diese Abschnitte von dieser EP-A- werden als Teil der vorliegenden Erfindung angesehen.Optionally costabilizers to be added to the stabilizer mixture of the invention are preferably further light stabilizers, for example those of the 2-hydroxyphenylbenzotriazole, 2-hydroxyphenyltriazine, benzophenone or oxalanilide classes, e.g. B. as in EP-A-453,396 . EP-A-434 608 . U.S.-A-5,298,067 . WO94 / 18278 . GB-A-2 297 091 and WO96 / 28431 described, and / or further hindered amines, by 2,2,6,6-tetraalkylpiperidine, the at least one group of the formula

wherein G contains hydrogen or methyl, in particular hydrogen, are derived; Examples of tetraalkylpiperidine derivatives which can be used as costabilizers with mixtures according to the invention are disclosed in US Pat EP-A-356 677 , Pages 3-17, sections a) to f). These sections of this EP-A are considered part of the present invention.

Also of particular interest is the use of the novel mixtures comprising compounds of formula IIIa as stabilizers for coatings, for example for paints. The invention therefore also relates to those compositions whose component (A) is a film-forming binder for coatings.

The new coating composition preferably comprises 0.01-10 parts by weight of (B), more preferably 0.05-10 parts by weight of (B), especially 0.1-5 parts by weight of (B), per 100 parts by weight of solid binder (A).

Multilayer systems are equally possible here, wherein the concentration of the novel stabilizer (component (B)) in the outer layer can be relatively high, for example 1 to 15 parts by weight (B), especially 3-10 parts by weight (B), per 100 parts by weight solid Binder (A).

The use of the novel stabilizer in coatings is accompanied by the further advantage of preventing delamination, that is, delamination of the coating from the substrate. This advantage is particularly important in the case of metal substrates, including multilayer systems on metal substrates.

The binder (component (A)) may, in principle, be any binder commonly used in the industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pages 368-426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) may be a cold-hardenable or heat-curable binder; the addition of a curing catalyst may be advantageous. Suitable catalysts which accelerate the curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, page 469, VCH Verlagsgesellschaft, Weinheim 1991.

Preferred are coating compositions in which component (A) is a binder comprising a functional acrylate resin and a crosslinking agent.

• 1. Anstrichstoffe, die auf kalt oder heiß vernetzbaren Alkyd-, Acrylat-, Polyester-, Epoxid- oder Melaminharzen oder Gemischen solcher Harze basieren, falls erwünscht unter Zusatz eines Härtungskatalysators;
• 2. Zweikomponenten-Polyurethan-Anstrichstoffe, die auf Hydroxyl enthaltenden Acrylat-, Polyester- oder Polyetherharzen und aliphatischen oder aromatischen Isocyanaten, Isocyanuraten oder Polyisocyanaten basieren;
• 3. Einkomponenten-Polyurethan-Anstrichstoffe, die auf blockierten Isocyanaten, Isocyanuraten oder Polyisocyanaten basieren, die während der Wärmebehandlung entblockiert werden, falls erwünscht unter Zusatz eines Melaminharzes;
• 4. Einkomponenten-Polyurethan-Anstrichstoffe, die auf Trisalkoxycarbonyltriazinvernetzer und einem Hydroxylgruppen enthaltenden Harz, wie Acrylat-, Polyester- oder Polyetherharzen, basieren;
• 5. Einkomponenten-Polyurethan-Anstrichstoffe, die auf aliphatischen oder aromatischen Urethanacrylaten oder Polyurethanacrylaten mit freien Aminogruppen in der Urethanstruktur und Melaminharzen oder Polyesterharzen basieren, falls erforderlich mit Härtungskatalysator;
• 6. Zweikomponenten-Anstrichstoffe, die auf (Poly)ketiminen und aliphatischen oder aromatischen Isocyanaten, Isocyanuraten oder Polyisocyanaten basieren;
• 7. Zweikomponenten-Anstrichstoffe, die auf (Poly)ketiminen oder einem ungesättigten Acrylatharz oder einem Polyacetoacetatharz oder einem Methacrylamidoglycolatmethylester basieren;
• 8. Zweikomponenten-Anstrichstoffe, die auf Carboxyl- oder Amino-enthaltenden Polyacrylaten und Polyepoxiden basieren;
• 9. Zweikomponenten-Anstrichstoffe, die auf Anhydridgruppen enthaltenden Acrylatharzen und einer Polyhydroxy- oder Polyaminokomponente basieren;
• 10. Zweikomponenten-Anstrichstoffe, die auf Acrylatenthaltenden Anhydriden und Polyepoxiden basieren;
• 11. Zweikomponenten-Anstrichstoffe, die auf (Poly)oxazolinen und Acrylatharzen, die Anhydridgruppen enthalten oder ungesättigten Acrylatharzen oder aliphatischen oder aromatischen Isocyanaten, Isocyanuraten oder Polyisocyanaten basieren;
• 12. Zweikomponenten-Anstrichstoffe, die auf ungesättigten Polyacrylaten und Polymalonaten basieren;
• 13. thermoplastische Polyacrylat-Anstrichstoffe, die auf thermoplastischen Acrylatharzen oder äußerlich vernetzten Acrylatharzen in Kombination mit veretherten Melaminharzen basieren;
• 14. Anstrichstoffsysteme, die auf Siloxan-modifizierten oder Fluor-modifizierten Acrylatharzen basieren.

Examples of coating compositions containing special binders are:

• 1. paints based on cold or hot crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if desired with the addition of a curing catalyst;
• 2. Two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
• 3. one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are unblocked during the heat treatment, if desired with the addition of a melamine resin;
• 4. One-component polyurethane paints based on trisalkoxycarbonyl triazine crosslinkers and a hydroxyl group-containing resin such as acrylate, polyester or polyether resins;
• 5. one-component polyurethane paints based on aliphatic or aromatic urethane acrylates or polyurethane acrylates having free amino groups in the urethane structure and melamine resins or polyester resins, if necessary with curing catalyst;
• 6. two-component paints based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
• 7. Two-component paints based on (poly) ketimines or an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
• 8. Two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides;
• 9. Two-component paints based on anhydride group-containing acrylate resins and a polyhydroxy or polyamino component;
• 10. Two-component paints based on acrylate-containing anhydrides and polyepoxides;
• 11. Two-component paints based on (poly) oxazolines and acrylate resins containing anhydride groups or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
• 12. Two-component paints based on unsaturated polyacrylates and polymalonates;
• 13. thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinked acrylate resins in combination with etherified melamine resins;
• 14. Paint systems based on siloxane-modified or fluorine-modified acrylate resins.

In addition to components (A) and (B), the coating composition of the invention preferably comprises as component (C) a hindered amine light stabilizer, 2- (2-hydroxyphenyl) -1,3,5-triazine and / or 2-hydroxyphenyl 2H-benzotriazole type, for example, as mentioned above in Sections 2.1, 2.6 and 2.8. Further examples of 2- (2-hydroxyphenyl) -1,3,5-triazine type light stabilizers, which are advantageously added, can be found, for example, in the publications US-A-4,619,956 . EP-A-434 608 . US-A-5,198,498 . U.S. Patent 5,322,868 . US-A-5,369,140 . U.S.-A-5,298,067 . WO94 / 18278 . EP-A-704 437 . GB-A-2 297 091 . WO96 / 28431 being found. Of particular technical interest is the addition of 2- (2-hydroxyphenyl) -1,3,5-triazines and / or 2-hydroxyphenyl-2H-benzotriazoles, especially the 2- (2-hydroxyphenyl) -1,3,5- triazines.

Component (C) is preferably added in an amount of 0.05-5 parts by weight per 100 parts by weight of the solid binder.

In addition to the components (A), (B) and if used (C), the coating composition may also contain other components; Examples are solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and / or leveling agents. Examples of possible components are those given in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A18, pages 429-471, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and / or phosphines. Examples of organometallic compounds are metal carboxylates, in particular those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, in particular those of the metals Al, Ti or Zr, or organometallic compounds, such as organotin compounds.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.

Examples of metal chelates are aluminum, titanium or zirconium chelates of acetylacetone, ethylacetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.

Examples of amines are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, e.g. B. trimethylbenzylammonium chloride.

Amino-containing resins are at the same time a binder and a curing catalyst. Examples of these are amino groups-containing acrylate copolymers.

The curing catalyst used may also be a phosphine, for example triphenylphosphine.

The novel coating compositions may also be radiation curable coating compositions. In this case, the binder substantially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds which can be cured after exposure to actinic radiation, that is, converted to a high molecular weight crosslinked form. When the system is UV curing, it generally also contains a photoinitiator. Corresponding systems are described in the above-mentioned publication Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A18, pages 451-453. In radiation-curable coating compositions, the novel stabilizers can also be used without the addition of sterically hindered amines.

The coating compositions according to the invention can be applied to any desired substrates, for example metal, wood, plastic or ceramic materials. They are preferably used as a topcoat for automotive coatings. If the top layer comprises two layers of which the bottom layer is pigmented and the top layer is unpigmented, the new coating composition can be used for either the top or bottom layers or for both layers, but preferably for the top layer.

The novel coating compositions can be applied to the substrates by conventional methods such as brushing, spraying, pouring, dipping or electrophoresis; See also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A18, pages 491-500.

Depending on the binder system, the coatings may be cured at room temperature or by heating. The coatings are preferably cured at 50-150 ° C and, in the case of powder coatings or coil coatings, also at higher temperatures.

The coatings obtained according to the invention have excellent resistance to the damaging effects of light, oxygen and heat, in particular the good light stability and weather resistance of the coatings thus obtained should be mentioned for these paints.

The invention therefore also relates to a coating, in particular a paint, which is stabilized against the damaging effects of light, oxygen and heat by a proportion of the compound of the formula F according to the invention. The paint is preferably a topcoat for motor vehicles. The invention further relates to a method of stabilizing a coating based on organic polymers against damage by light, oxygen and / or heat, mixing a mixture comprising a compound of the formula F with the coating composition and relates to the use of a coating A mixture comprising a compound of formula F in coating compositions as stabilizers against damage by light, oxygen and / or heat.

The coating compositions may contain an organic solvent or solvent mixture in which the binder is soluble. The coating composition may otherwise be an aqueous solution or dispersion. The carrier may also be a mixture of organic solvent and water. The coating composition may be a high solids paint or may be solventless (for example, a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, A18, pages 438-444. The additive according to the invention can therein, for example, as in EP-A-856 563 , especially page 22, column 21, to page 26, column 29, and the literature cited in this publication. The powder coating material may also be in the form of a powder slurry (dispersion of the powder, preferably in water).

• 1. Carboxy- oder Hydroxy-funktionalisierte Polyesterharze, die auf Monomeren, wie Terephthalsäure, Isophthalsäure, Neopentylglycol, 2-Methyl-1,3-propandiol, Tris-1,1,1-(hydroxymethyl)propan, usw., basieren.
• 2. Epoxidharze, die auf Bisphenolen, wie Bisphenol A- oder Novolak^®-Epoxidharzen für thermische oder UV-Härtung mit kationischen Fotostartern basieren.
• 3. Hydroxy-, Carboxy- oder Glycidyl-funktionalisierte Acrylatpolymere und Copolymere. Geeignete Comonomere schließen Styrol, Alkylmethacrylate, Acrylamid, Acrylnitril, usw., ein.
• 4. Ungesättigte Polyesterharze für UV-härtbare Pulverbeschichtungen, die im allgemeinen im Zusammenhang mit mehrfach funktionellen Vinylethern oder Acrylatestern verwendet werden.

Examples of resins for powder coatings are:

• 1. Carboxy- or hydroxy-functionalized polyester resins based on monomers such as terephthalic acid, isophthalic acid, neopentyl glycol, 2-methyl-1,3-propanediol, tris-1,1,1- (hydroxymethyl) propane, etc.
• 2. Epoxy resins based on bisphenols, such as bisphenol A or novolac ^® -Epoxidharzen for thermal or UV cure with cationic photoinitiators.
• 3. Hydroxy-, carboxy- or glycidyl-functionalized acrylate polymers and copolymers. Suitable comonomers include styrene, alkyl methacrylates, acrylamide, acrylonitrile, etc.
• 4. Unsaturated polyester resins for UV-curable powder coatings, which are generally used in conjunction with polyfunctional vinyl ethers or acrylate esters.

• 1) Polyfunktionelle Epoxyverbindungen, wie Epoxidharz, Triglycidylisocyanurat, epoxidierte ungesättigte Fettsäureester (wie Uranox^® Harze von DSM) und Ester und Ether von Glycidol (wie Araldit^® PT910 von Ciba Specialty Chemicals).
• 2) β-Hydroxyalkylamide, wie Primid^® Arten XL552 und QM1260 von Ems Chemie.
• 3) Derivate von Melamin, Benzoguanimin und Glycoluril, wie Powderlink^® 1174 von American Cyanamid.

Powder coatings based on carboxy-functional resins are generally used in conjunction with crosslinkers of the following classes:

• 1) polyfunctional epoxy compounds such as epoxy resin, triglycidyl isocyanurate, epoxidized unsaturated fatty acid ester (such as Uranox ^® resins from DSM), and esters and ethers of glycidol (such as Araldit ^® PT910 from Ciba Specialty Chemicals).
• 2) β-hydroxyalkylamides, such as Primid ^® XL552 and QM1260 from Ems types chemistry.
• 3) derivatives of melamine, benzoguanimine and glycoluril, such as Powderlink ^® 1174 from American Cyanamid.

Crosslinking agents for hydroxy-functional resins include anhydrides and especially blocked diisocyanates and uretdiones, etc.

Powder coatings based on epoxy-functional resins are generally used together with crosslinking agents such as diacids (such as 1,12-dodecanedioic acid), carboxy-functional polyesters, carboxy-functional copolymers of acrylates and methacrylates, anhydrides (such as those of 1,12- Dodecanedioic anhydride).

Other additives that can be used with the compounds of the invention in powder coatings include degassing agents, flow aids, tribo-discharge additives, curing catalysts, sensitizers, cationic and radical photoinitiators, and typical liquid paint additives.

A particular advantage of the compounds of the invention is their low basicity, since basic compounds often catalyze the crosslinking reactions of powder coatings, causing poor flow and degassing and reduced storage stability. This is particularly useful in high reactivity formulations such as glycidyl methacrylate functional acrylic resins. Here, the combination of the compounds of the present invention with UV absorbers, particularly the hydroxyphenyltriazine class, can be used to improve the weatherability without causing catalysis. In other binder systems and with other classes of UV absorbers, such as those already mentioned as of particular interest for use in automotive paints, synergistic effects on weatherability have also been found.

The compounds of this invention can also be used in powder coatings to improve oxidation stability and to reduce yellowing on curing and overheating on drying. Here, not only the low basicity is advantageous but also the ability of the hindered morpholinones to prevent and resist yellowing caused by nitrogen oxides in gas firing furnaces. The application, in particular together with phosphite and phosphonite costabilizers, as in EP-A-816 442 and dialkyl esters of dithiopropionic acid is particularly advantageous. The compounds of this invention, if appropriate, may also be used to stabilize polyester during manufacture and in stages of its subsequent use.

The pigments may be inorganic, organic or metallic pigments. The novel coating compositions preferably contain no pigments and are used as a clearcoat.

Likewise preferred is the use of the coating composition as a topcoat for automotive industry applications, especially as a pigmented or unpigmented topcoat of the paint finish. However, their use for underlying coatings is also possible.

Some products of the present process are new compounds.

The present invention therefore also relates to a compound of the formula I, in particular a compound of the formula Ia, wherein R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₃ -C _{8 is} alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group, C ₆ -C ₁₂ aryl substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, and wherein at least one of R ₅ , R ₆ , R ₇ , R ₈ and R _{9 is} not H. The present invention also relates to a compound of the formula I, in particular a compound of the formula Ia, in which R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl , C ₅ -C ₁₂ aryl, an electron withdrawing group, C ₆ -C ₁₂ aryl substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, and all other symbols such as are defined above.

worin der Index n im Bereich von 1 bis 15, insbesondere im Bereich 3–9 liegt;
R₅ bis R₉ wie für Formel I definiert sind;
R₁₂ C₂-C₁₂-Alkylen, C₄-C₁₂-Alkenylen, C₅-C₇-Cycloalkylen, C₅-C₇-Cycloalkylendi(C₁-C₄-alkylen), C₁-C₄-Alkylendi(C₅-C₇-cycloalkylen), Phenylendi(C₁-C₄-alkylen) oder C₄-C₁₂-Alkylen, unterbrochen durch 1,4-Piperazindiyl, -O- oder >N-X₁, wobei X₁ C₁-C₁₂-Acyl oder (C₁-C₁₂-Alkoxy)carbonyl darstellt oder eine der nachstehend für R₁₄ angegebenen Definitionen, mit Ausnahme von Wasserstoff, aufweist oder R₁₂ eine Gruppe der Formel (Ib') oder (Ic') darstellt,

X₂ C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Phenyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist, darstellt und
die Reste X₃ unabhängig voneinander C₂-C₁₂-Alkylen darstellen;
die Reste A unabhängig voneinander -OR₁₃, -N(R₁₄)(R₁₅) oder eine Gruppe der Formel (Id') darstellen;

R₁₃, R₁₄ und R₁₅, die gleich oder verschieden sind, Wasserstoff, C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; C₃-C₁₈-Alkenyl, Phenyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Tetrahydrofurfuryl oder C₂-C₄-Alkyl, das in 2-, 3- oder 4-Stellung mit -OH, C₁-C₈-Alkoxy, Di(C₁-C₄-alkyl)amino oder einer Gruppe der Formel (Ie') substituiert ist;

wobei Y -O-, -CH₂-, -CH₂CH₂- oder >N-CH₃ darstellt, bedeuten
oder -N(R₁₄)(R₁₅) zusätzlich eine Gruppe der Formel (Ie') darstellt;
X -O- oder >N-R₁₆ darstellt;
R₁₆ Wasserstoff, C₁-C₁₈-Alkyl, C₃-C₁₈-Alkenyl, C₅-C₁₂-Cycloalkyl, das unsubstituiert oder mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; C₇-C₉-Phenylalkyl, das unsubstituiert oder am Phenyl mit 1, 2 oder 3 C₁-C₄-Alkyl substituiert ist; Tetrahydrofurfuryl, eine Gruppe der Formel (If')

oder C₂-C₄-Alkyl, das in der 2-, 3- oder 4-Stellung mit -OH substituiert ist, C₁-C₈-Alkoxy, Di(C₁-C₄-alkyl)amino oder eine Gruppe der Formel (Ie') darstellt;
R₁₁ eine der für R₁₆ angegebenen Definitionen aufweist und
die Reste B unabhängig voneinander eine der für A angegebenen Definitionen aufweisen;
und worin in den einzelnen wiederkehrenden Einheiten der Formel (Ia) jeder der Reste B, R₁₁ und R₁₂ gleiche oder verschiedene Bedeutungen aufweisen können.Preferred compounds of the formula I are those of the formula Ia

wherein the index n is in the range of 1 to 15, in particular in the range 3-9;
R ₅ to R _{9 are} as defined for formula I;
R _{12 is} C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkenylene, C ₅ -C ₇ -cycloalkylene, C ₅ -C ₇ -cycloalkylenedi (C ₁ -C ₄ -alkylene), C ₁ -C ₄ -alkylenedi (C ₅ -C ₇ -cycloalkylene), phenylenedio (C ₁ -C ₄ -alkylene) or C ₄ -C ₁₂ -alkylene interrupted by 1,4-piperazinediyl, -O- or> NX ₁ , where X _{1 is} C ₁ C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or has one of the definitions given below for R ₁₄ , with the exception of hydrogen, or R _{12 represents} a group of the formula (Ib ') or (Ic') .

X _{2 is} C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; Phenyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ -alkyl, and
the radicals X ₃ independently of one another represent C ₂ -C ₁₂ -alkylene;
each A independently represents -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of formula (Id ');

R ₁₃ , R ₁₄ and R ₁₅ , which are the same or different, are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl is; C ₃ -C ₁₈ alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or C ₂ -C ₄ -alkyl which is in the 2-, 3- or 4-position with -OH, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of the formula ( Ie ') is substituted;

where Y is -O-, -CH ₂ -, -CH ₂ CH ₂ - or> N-CH ₃ , mean
or -N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie ');
X represents -O- or> NR ₁₆ ;
R _{16 is} hydrogen, C ₁ -C ₁₈ -alkyl, C ₃ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (If ')

or C ₂ -C ₄ -alkyl substituted with -OH in the 2, 3 or 4 position, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of Represents formula (Ie ');
R _{11 has} one of the definitions given for R ₁₆ and
the radicals B independently of one another have one of the definitions given for A;
and in which individual repeating units of the formula (Ia) each of the radicals B, R ₁₁ and R _{12 may have} identical or different meanings.

worin R eine organische verbindende Gruppe der Formel

darstellt;
E₂ -CO- oder -(CH₂)_p-, worin p 0, 1 oder 2 ist, darstellt;
E₁ ein Kohlenstoffatom, das zwei Reste R₂₄ und R₂₅ trägt, darstellt, oder >N-R₂₅ ist oder Sauerstoff ist und R₂₄ und R₂₅ Wasserstoff oder einen organischen Rest darstellen, dadurch gekennzeichnet, daß die verbindende Gruppe R insgesamt 2-500 Kohlenstoffatome enthält und zusammen mit den Kohlenstoffatomen, die direkt mit ihr verbunden sind, und dem Stickstoffatom eine substituierte, 5-, 6- oder 7-gliedrige, cyclische Ringstruktur bilden;
R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen;
R₅, R₆, R₇, R₈ und R₉ unabhängig voneinander H, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen;
R₂₀ und R₂₁ Halogen darstellen und
R₂₂ und R₂₃ Wasserstoff darstellen oder zusammen eine chemische Bindung darstellen,
mit der Maßgabe, daß R in Formel IIIc nicht die verbindende Gruppe

darstellt, worin R₂₄ und R₂₅ zusammen =O darstellen, oder worin R₂₄ Wasserstoff darstellt und R₂₅ Wasserstoff, OH oder Alkanoyloxy, das mit Phenoxy oder Alkylphenoxy substituiert ist, darstellt.Further novel products according to the invention correspond to formulas IIIc, IVa and Va

wherein R is an organic linking group of the formula

represents;
E _{2 is} -CO- or - (CH ₂ ) _p - wherein p is 0, 1 or 2;
E _{1 represents} a carbon atom bearing two radicals R ₂₄ and R ₂₅ , or> NR ₂₅ or oxygen and R ₂₄ and R _{25 represent} hydrogen or an organic radical, characterized in that the linking group R is a total of 2-500 Containing carbon atoms and together with the carbon atoms connected directly to it and the nitrogen atom form a substituted, 5-, 6- or 7-membered cyclic ring structure;
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;
R ₂₀ and R _{21 represent} halogen and
R ₂₂ and R _{23 represent} hydrogen or together represent a chemical bond,
with the proviso that R in formula IIIc is not the linking group

wherein R ₂₄ and R ₂₅ together represent = O, or wherein R _{24 represents} hydrogen and R _{25 represents} hydrogen, OH or alkanoyloxy which is substituted by phenoxy or alkylphenoxy.

When E _{1 is} substituted carbon, E _{2 is} mainly - (CH ₂ ) _p -, especially CH ₂ ; when E _{1 is} oxygen or NR ₂₅ , E _{2 is} mainly carbonyl.

übereinstimmt,
worin p 0, 1 oder 2 ist;
R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen, oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen;
R₅ und R₆ unabhängig voneinander H oder Methyl darstellen und R₇, R₈ und R₉ unabhängig voneinander C₁-C₄-Halogenalkyl, Phenyl, Vinyl, Nitro, CN, COOR₁₀, worin R₁₀ C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl oder Phenyl bedeutet, darstellen;
R₂₄ und R₂₅ unabhängig voneinander Wasserstoff oder einen wie bereits definierten, organischen Rest darstellen und
R₂₆ Wasserstoff oder einen organischen Rest darstellt, der zusammen mit der Übrigen Struktur von Formel (VIb) einen C₂-C₅₀₀-Kohlenwasserstoffrest bildet, welcher 1-200 Heteroatome, ausgewählt aus Stickstoff, Sauerstoff, Phosphor, Schwefel, Silicium und Halogen, enthält.Thus, a compound of the formula IIIc, IVa or Va is preferred in which R is a bivalent C ₇ -C ₅₀₀ -hydrocarbon or a C ₂ -C _500- hydrocarbon radical containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, Sulfur, silicon and halogen, means and with the structure

matches,
wherein p is 0, 1 or 2;
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl, or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ - C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
R ₅ and R ₆ independently of one another represent H or methyl and R ₇ , R ₈ and R ₉ independently of one another are C ₁ -C ₄ -haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ , in which R _{10 is} C ₁ -C ₁₂ - Alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl;
R ₂₄ and R ₂₅ independently of one another represent hydrogen or an organic radical as already defined, and
R _{26 represents} hydrogen or an organic radical which, together with the remainder of the structure of formula (VIb), forms a C ₂ -C _500- hydrocarbon radical which contains 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen, contains.

Most preferred is a compound of formula IIIc, IVa or Va wherein
R ₅ and R _{6 are} independently H or methyl and R ₇ , R ₈ and R _{9 are} independently C ₁ -C ₄ bromoalkyl, phenyl, CN, COOR ₁₀ , wherein R _{10 is} C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ -cycloalkyl or phenyl, in particular wherein R ₅ , R ₆ , R ₇ , R ₈ and R _{9 are} hydrogen;
R ₂₀ and R _{21 are} bromo; and
if R agrees with the structure of formula VIa,
p 1 and R ₁ , R ₂ , R ₃ and R _{4 are} independently methyl or ethyl;
if R agrees with the structure of formula VIb,
R ₁ , R ₂ , R ₃ and R _{4 are} independently methyl or ethyl, or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ cycloalkyl, or R ₃ and R ₄ together with the carbon atom to which they are attached are C ₅ -C ₁₂ cycloalkyl;
if R agrees with the structure of formula VIc,
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl, or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ - C ₁₂ cycloalkyl, or R ₃ and R ₄ together with the carbon atom to which they are attached are C ₅ -C ₁₂ cycloalkyl.

worin R einen C₇-C₅₀₀-Kohlenwasserstoffrest, der 1-200 Heteroatome, ausgewählt aus Stickstoff, Sauerstoff, Phosphor, Schwefel und Halogen enthält, darstellt und zusammen mit den zwei Kohlenstoffatomen und dem Stickstoffatom eine substituierte 5- oder 6-gliedrige, cyclische Ringstruktur bildet und R₁, R₂, R₃ und R₄ wie vorstehend definiert sind, mit der Maßgabe, daß R nicht die Formel IIIc vervollständigt, unter Bildung der Struktur der Formel

Special emphasis deserves a compound of Formula IIIc

wherein R is a C ₇ -C ₅₀₀ hydrocarbon radical containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, and together with the two carbon atoms and the nitrogen atom is a substituted 5- or 6-membered cyclic Ring structure and R ₁ , R ₂ , R ₃ and R _{4 are} as defined above, with the proviso that R does not complete the formula IIIc to form the structure of the formula

Particularly preferred is a compound of formula IIIc shown above.

worin
n₁ eine Zahl von 1 bis 4 ist, G und G₁ unabhängig voneinander Wasserstoff oder Methyl darstellen,
G₁₁ n-Propoxy, O-CH=C=CH₂, O-CH=CH-CH₃ oder halogeniertes n-Propoxy, insbesondere n-Propoxy oder bromiertes n-Propoxy, darstellt;
G₁₂, wenn n₁ 1 ist, C₁-C₁₈-Alkyl, das nicht unterbrochen oder durch ein oder mehrere Sauerstoffatome unterbrochen ist, Cyanoethyl, Benzoyl, Glycidyl, einen einwertigen Rest von einer aliphatischen, cycloaliphatischen, ungesättigten oder aromatischen Carbonsäure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen einwertigen Silylrest, vorzugsweise einen Rest von einer aliphatischen Carbonsäure mit 2 bis 18 Kohlenstoffatomen, von einer cycloaliphatischen Carbonsäure mit 7 bis 15 Kohlenstoffatomen oder von einer α,β-ungesättigten Carbonsäure mit 3 bis 5 Kohlenstoffatomen darstellt, wobei jede Carbonsäure in der aliphatischen, cycloaliphatischen oder aromatischen Einheit, falls vorliegend, mit 1 bis 3 Gruppen -COOZ₁₂, worin Z₁₂ H, C₁-C₂₀-Alkyl, C₃-C₁₂-Alkenyl, C₅-C₇-Cycloalkyl, Phenyl oder Benzyl bedeutet, substituiert sein kann;
G₁₂, wenn n₁ 2 ist, C₂-C₁₂-Alkylen, C₄-C₁₂-Alkenylen, Xylylen, einen zweiwertigen Rest von einer aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, vorzugsweise einen Rest von einer aliphatischen Dicarbonsäure mit 2 bis 36 Kohlenstoffatomen oder von einer cycloaliphatischen oder aromatischen Dicarbonsäure mit 8-14 Kohlenstoffatomen oder von einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbaminsäure mit 8-14 Kohlenstoffatomen darstellt, wobei jede Dicarbonsäure in der aliphatischen, cycloaliphatischen oder aromatischen Einheit mit einer oder zwei Gruppen -COOZ₁₂ substituiert sein kann;
G₁₂, wenn n₁ 3 ist, einen dreiwertigen Rest von einer aliphatischen, cycloaliphatischen oder aromatischen Tricarbonsäure, die in der aliphatischen, cycloaliphatischen oder aromatischen Einheit mit -COOZ₁₂ substituiert sein kann, von einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure darstellt oder einen dreiwertigen Silylrest darstellt;
und G₁₂, wenn n₁ 4 ist, einen vierwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure darstellt;
R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen;
G Wasserstoff oder Methyl darstellt;
G₁ und G₂ unabhängig voneinander Wasserstoff, Methyl, darstellen oder zusammen einen Substituenten =O darstellen; und
G₃ eine direkte Bindung oder Methylen bedeutet,
offene Bindungen der Formeln (3) und (4) an ein Kohlenstoff-, Stickstoff- oder Sauerstoffatom eines wie vorstehend definierten organischen Restes gebunden sind,
G₁₃ Wasserstoff, C₁-C₁₂-Alkyl, C₂-C₅-Hydroxyalkyl, C₅-C₇-Cycloalkyl, C₇-C₈-Aralkyl, C₁-C₁₈-Alkanoyl, C₃-C₅-Alkenoyl, Benzoyl oder eine Gruppe der Formel (1b-1)

darstellt,
n₂ die Zahl 1, 2 oder 3 ist;
und G₁₄, wenn n₂ 1 ist, Wasserstoff, C₁-C₁₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₇-Cycloalkyl, C₁-C₄-Alkyl, das mit einer Hydroxyl-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiert ist, Glycidyl, eine Gruppe der Formel -CH₂-CH(OH)-Z oder der Formel -CONH-Z, worin Z Wasserstoff, Methyl oder Phenyl bedeutet, darstellt;
G₁₄, wenn n₂ 2 ist, C₂-C₁₂-Alkylen, C₆-C₁₂-Arylen, Xylylen, eine Gruppe -CH₂-CH(OH)-CH₂ oder eine Gruppe -CH₂-CH(OH)-CH₂-O-D-O-, worin D C₂-C₁₀-Alkylen, C₆-C₁₅-Arylen, C₆-C₁₂-Cycloalkylen bedeutet, darstellt, oder, mit der Maßgabe, daß G₁₃ nicht Alkanoyl, Alkenoyl oder Benzoyl darstellt, G₁₄ alternativ 1-Oxo-C₂-C₁₂-alkylen, einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure oder alternativ die Gruppe -CO- darstellen kann,
G₁₄, wenn n₂ 3 ist, eine Gruppe

darstellt, oder, wenn n₂ 1 ist, G₁₃ und G₁₄ zusammen den zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure bedeuten können.Thus, the new sterically hindered amine usually corresponds to the formulas (1a), (1b) or (2a) or contains at least one group of the formula (3) or (4)

wherein
n _{1 is} a number from 1 to 4, G and G ₁ independently of one another represent hydrogen or methyl,
G _{11 is} n-propoxy, O-CH = C = CH ₂ , O-CH = CH-CH ₃ or halogenated n-propoxy, especially n-propoxy or brominated n-propoxy;
G ₁₂ when n _{1 is} 1, C ₁ -C ₁₈ alkyl not interrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms or of an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms, each carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety, if present, with 1 to 3 groups -COOZ ₁₂ , wherein Z ₁₂ H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₂ -alkenyl, C ₅ -C ₇ -cycloalkyl, Phenyl or benzyl, may be substituted;
G ₁₂ , when n _{1 is} 2, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical , preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms or of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, wherein each dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety may be substituted with one or two groups -COOZ ₁₂ ;
G ₁₂ , when n is ₁ , represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety with -COOZ ₁₂ , of an aromatic tricarbamic acid or a phosphorus-containing acid, or a trivalent silyl group;
and G ₁₂ , when n _{1 is} 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl;
G represents hydrogen or methyl;
G ₁ and G _{2 are} independently hydrogen, methyl, or together represent a substituent = O; and
G _{3 is} a direct bond or methylene,
open bonds of the formulas (3) and (4) are bonded to a carbon, nitrogen or oxygen atom of an organic radical as defined above,
G _{13 is} hydrogen, C ₁ -C ₁₂ -alkyl, C ₂ -C ₅ -hydroxyalkyl, C ₅ -C ₇ -cycloalkyl, C ₇ -C ₈ -aralkyl, C ₁ -C ₁₈ -alkanoyl, C ₃ -C ₅ - Alkenoyl, benzoyl or a group of formula (1b-1)

represents,
n _{2 is} the number 1, 2 or 3;
and G ₁₄ , when n is ₂ , is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, C ₁ -C ₄ alkyl which is hydroxyl, Cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CH ₂ -CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl;
G ₁₄ , when n _{2 is} 2, C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, a group -CH ₂ -CH (OH) -CH ₂ or a group -CH ₂ -CH (OH ) -CH ₂ -ODO-, wherein DC is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₅ -arylene, C ₆ -C ₁₂ -cycloalkylene, or, provided that G _{13 is} not alkanoyl, alkenoyl or Benzoyl, G _{14 may} alternatively be 1-oxo-C ₂ -C ₁₂ -alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or alternatively may represent the group -CO-,
G ₁₄ , if n _{2 is} 3, a group

represents, or when n is ₂ 1, G ₁₃ and G ₁₄ together may denote the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Preferred novel hindered amines of Formula IIIc are as described in (b ') - (j') above and preferences are given herein. The novel compounds of formula IIIc are useful as stabilizers for organic material against degradation by light, oxygen and / or heat. The materials to be stabilized z. As oils, fats, waxes, cosmetics or biocides. Of particular interest is the use in polymeric materials such as plastics, rubbers, coating materials, photographic materials or adhesives; Examples are organic polymers as described above, and reprographic, in particular color photographic material, such as in GB-A-2 319 523 . DE-A-197 50 906 , Page 23, line 20, to page 105, line 32, or in US-A-5 538 840 , Column 25, line 60, to column 106, line 31; these parts of US-A-5 538 840 are incorporated by this reference herein.

Further preferences are described above for the compounds of formulas I and III.

Fp.

Schmelzpunkt oder -bereich;

Mn

zahlenmittleres Molekulargewicht (g/Mol);

Mw

gewichtsmittleres Molekulargewicht (g/Mol);

GPC

Gelpermeationschromatographie.

Beispiel 1: Herstellung der Ausgangsverbindung der Formel

The following examples illustrate the invention. All parts and percentages in the examples, as in the remainder of the specification and in the claims, are by weight unless otherwise indicated. Room temperature means a temperature in the range of 20-30 ° C, unless stated otherwise. In the examples, the following abbreviations are used:

Mp.

Melting point or range;

Mn

number average molecular weight (g / mol);

mw

weight average molecular weight (g / mol);

GPC

Gel permeation chromatography.

Example 1: Preparation of the starting compound of the formula

Step 1: A solution of 74.3 g (0.35 mol) of N- (2,2,6,6-tetramethyl-4-piperidinyl) -n-butylamine in 50 ml of water slowly becomes a solution at 0 ° C of 64.5 g (0.35 mol) of cyanuric chloride in 500 ml of xylene, maintaining the temperature during the addition and for an additional 1 hour. After 2 hours at room temperature, the mixture is cooled to 0 ° C and an aqueous solution of 14.7 g (0.368 mol) of sodium hydroxide in 50 ml of water is added. After ½ hour at 0 ° C and a further 2 hours at room temperature, the aqueous solution is separated and 69.2 g (0.175 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1 6-hexanediamine is added.

The mixture is heated at 50 ° C for 1 hour and 48.4 g (0.35 mole) of ground potassium carbonate are added and heated to 60 ° C for 4 hours.

After washing with water, the organic phase is concentrated under vacuum at 60-70 ° C / 10 mbar, with 250 ml of xylene are removed. 138.1 g (0.35 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine are added and the mixture is heated to 150 ° C for 2 hours , cooled again and 14 g (0.35 mol) of ground sodium hydroxide are added.

The mixture is heated to 140 ° C. for a further 4 hours, the remaining water of reaction being removed azeotropically and heated to 160 ° C. for a further 4 hours.

After cooling to 60 ° C, the mixture is diluted with 300 ml of xylene, filtered and washed three times with 100 ml of ethylene glycol.

This solution can be used to isolate the compound described in Example 6.

Step 2: After concentrating under vacuum at 60 ° C / 10 mbar, 54.4 g (0.147 mol) of 2-chloro-4,6-bis (dibutylamino) -1,3,5-triazine are added.

The mixture is heated at 140 ° C for 3 hours and 20.3 g (0.147 mol) of ground potassium carbonate are added, the mixture is heated to reflux and the reaction water is removed azeotropically.

The mixture is heated at 160 ° C for 4 hours, a further 20.3 g (0.147 mol) of ground potassium carbonate are added and heated again to 160 ° C for 2 hours. After cooling to 60 ° C, the mixture is diluted with 300 ml of xylene, filtered and concentrated under vacuum at 140 ° C / 1 mbar. A solid having a melting range of 130-136 ° C. is obtained after drying, Mn (according to GPC): 2830 g / mole. Example 2: Method of the present invention; Preparation of the compound of the formula

Step 1: Into a 1 liter stainless steel autoclave with heating and mechanical stirrer are fed: a solution of 150 g (0.05 mol) of the product of Example 1 in 400 ml of xylene, 66.5 g (0.55 mol ) Allyl bromide and 114 g (0.825 mol) of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours and cooled to 60 ° C. 300 ml of water are added and the mixture is stirred vigorously. The organic layer is then collected and introduced into a 1 liter round bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel. After cooling to -15 ° C 128 g of a solution of 32 weight percent peracetic acid in acetic acid are added within 30 minutes with stirring. The temperature is allowed to rise to 0 ° C and the reaction mixture is allowed to react for 4 hours.

A solution of 250 g of K ₂ CO ₃ in 500 ml of water is added and kept at 0 ° C for 30 minutes with stirring. The organic layer is collected, washed 3 times with 100 ml portions of water and dried over sodium sulfate.

Step 2: The solution is introduced into a 1 liter stainless steel autoclave. After adding 3 g of 5 wt .-% - platinum on carbon, the autoclave is filled with 40 bar of hydrogen and kept for a period of 6 hours at 70 ° C with stirring. Subsequently, the autoclave is cooled to 20 ° C and relieved. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. The product is obtained as a white solid, mp 127-135 ° C, Mn (GPC) = 3580 g / mol, Mw / Mn = 1.33. Example 3: Method of the present invention; Preparation of the compound of the formula

In a round bottom flask are fed: 20 g of 1-allyl-2,2,6,6-tetramethylpiperidin-4-ol, 40 ml of methanol, 118 g of H ₂ O ₂ solution at 35% (volume / volume).

The mixture is heated to 65 ° C, allowed to react for 5 hours, concentrated under vacuum until methanol is distilled off and 40 ml of CH ₂ Cl ₂ are added. The mixture is stirred and the organic layer is collected and concentrated. The product is obtained as a pale yellow oil.
¹ H NMR (300 MHz, _CDCl3) / ppm: 5.90 to 5.80 (m, 1H); 5.21-4.97 (m, 2H); 4.24 (m, 2H); 3.87 (m, 1H); 1.75 (m, 2H); 1.42 (m, 2H); 1.15 (s, 3H); 1.11 (s, 3H). Example 4a: Preparation of the compound of the formula

Into a stainless steel autoclave are introduced: 20 g of the product of Example 3, 0.2 g of Raney nickel and 100 ml of toluene; the autoclave is filled with 8 bar of hydrogen and kept under tubes at 25 ° C for a period of 8 hours. Then the autoclave is relieved, the catalyst removed by filtration and the mixture concentrated under vacuum. The product is obtained as a white solid. ¹ H NMR (300 MHz, _CDCl3) / ppm: 3.95 (m, 1H); 3.66 (t, 2H); 1.57 (m, 4H); 1.22 (m, 2H); 1.13 (s, 12H); 0.89 (t, 3H). Example 4b: Preparation of the compound of the formula

In a round bottom flask are fed: 20 g of the product of Example 4a, 10.6 g of methyl sebacate, 100 ml of xylene and 0.25 g of dibutyltin oxide.

The mixture is heated to 145 ° C, allowed to react for 6 hours with stirring, allowed to cool and concentrated under vacuum to give the above product as an oil.
¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H); 1.77 (m, 4H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6H). Further analytical data: HPLC determination: 80% Elemental analysis: C measured 67.6% calculated 68.4% H measured 10.6% calculated 10.8% N measured 4.7% charged 4.7% Example 5: Method of the present invention; Preparation of the compound of the formula

In a stainless steel autoclave, 20 g of sebacic acid-bis (2,2,6,6-tetramethylpiperidin-4-yl) ester (trade name: Tinuvin ^® 770), 24 g of allyl bromide, introduced 6 g of potassium carbonate and 100 ml of toluene; The mixture is heated to 120 ° C, allowed to react for 5 hours with stirring, cooled and filtered to remove the salts. The excess of allyl bromide is removed by distillation.

The solution is introduced into a round bottom flask and 8 g of m-chloroperbenzoic acid dissolved in 50 ml of toluene are added while maintaining the temperature below 25 ° C over a period of 30 minutes.

Then, a solution of 13 g of potassium carbonate in 100 ml of water is added to the reaction mixture and left under stirring for 30 minutes. The organic layer is collected and washed with potassium carbonate solution prepared as described above. The organic layer is then dried over sodium sulfate and introduced into a stainless steel autoclave. After addition of 1 g of 5 wt .-% - platinum on carbon, the autoclave is filled with 8 bar of hydrogen and kept at 25 ° C for 4 hours with stirring. After removal of the catalyst by filtration, the solution is concentrated under vacuum. The product is obtained as a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H); 1.77 (m, 4H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6H). Further analytical data: HPLC determination: 78% Elemental analysis: C measured 67.2% calculated 68.4% H measured 10.3% calculated 10.8% N measured 4.6% charged 4.7% Example 6: Intermediate of the formula

The preparation of the present compound follows the procedure described in Example 1 up to step 1. The solution obtained from step 1 is then concentrated at 140 ° C and 1 mbar and gives a solid, mp. 138-143 ° C, with a medium Mn (GPC) of 2555 g / mol. Example 7:

To a solution of 150 g of the product of Example 6 in 400 ml of xylene are added 66.5 g of allyl bromide and 114 g of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours and cooled to 60 ° C. 300 ml of water are added and the mixture is stirred vigorously. The organic layer is then collected, cooled to -15 ° C and 128 g of a solution of 32% by weight of peracetic acid in acetic acid are added over 30 minutes with stirring. The temperature is allowed to rise to 0 ° C and the reaction mixture allowed to react for 4 hours. A solution of 250 g of K ₂ CO ₃ in 500 ml of water is added with stirring and allowed to react at 0 ° C for 30 minutes. The organic layer is collected, washed 3 times with 100 ml portions of water and dried over sodium sulfate. The solution is fed into a 1 liter stainless steel autoclave. After the addition of 3 g of 5 wt .-% - platinum on carbon, the autoclave with 40 filled with hydrogen and kept at 70 ° C with stirring for a period of 6 hours. Subsequently, the autoclave is cooled to 20 ° C and relieved. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. The product is obtained as a white solid, mp 125-135 ° C, Mn (GPC) = 2979 g / mole. Example 8: Compound of the formula

To a solution of 93 g of 2-chloro-4,6-bis (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl)) - 1,3,5-triazine in 300 ml Toluene is added to 42 g of allyl bromide and 71.7 g of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 10 hours, cooled to 60 ° C and 300 ml of water are added with stirring. The organic layer is then collected and cooled to -5 ° C, 64 g of a solution of 39% by weight of peracetic acid in acetic acid are added over 30 minutes with stirring. The temperature is allowed to rise to 0 ° C and the reaction mixture is allowed to react for 2 hours. A solution of 90 g of sodium carbonate in 500 ml of water is added and kept at 0 ° C for 30 minutes with stirring. The organic layer is collected and dried over sodium sulfate. The solution is fed into a 1 liter stainless steel autoclave. After adding 3 g of 5 wt .-% - platinum on carbon, the autoclave is filled with 40 bar of hydrogen and kept for a period of 6 hours at 70 ° C with stirring. Subsequently, the autoclave is cooled to 20 ° C and relieved. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. The product is obtained as a white solid.
¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.97 (m, 2H); 3.67 (t, 4H); 3.29 (m, 4H); 1.80-1.30 (m, 20H); 1.31-1.08 (m, 28H); 0.92-0.80 (m, 12H). Example 9: Compound of the formula

A mixture composed of 64.5 g of the compound described in Example 8, 200 ml of xylene, 20.4 g of potassium carbonate and 4.6 g of N-1- [2- (3-aminopropylamino) ethyl] propane-1,3- Diamine is heated for 10 hours at 140 ° C, cooled to 20 ° C and washed with 200 ml of water. The collected organic layer is concentrated at 140 ° C and 1 mbar. The solid obtained has a mp in the range of 115-120 ° C. Example 10: Compound of the formula

To a solution of 30 g of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine in 240 ml of toluene are added 50 g of allyl bromide and 63 g of potassium carbonate. The resulting mixture is heated to 150 ° C and allowed to react for 6 hours, cooled to 20 ° C, filtered and the volume of the solution is reduced to 100 ml by evaporation of the solvent at 110 ° C and 1 mbar vacuum. 150 ml of toluene are added to the concentrate solution, and after cooling to -10 ° C., a solution of 82 g of m-chloroperbenzoic acid in 200 ml of toluene is added over a period of one hour with stirring. After heating the mixture to 0 ° C, a solution of 100 g of potassium carbonate in 300 ml of water is added with stirring and allowed to reach 20 ° C. The organic layer is collected, dried over sodium sulfate and hydrogenated at 40 bar hydrogen with 2 g of 5% platinum on carbon at 70 ° C for 8 hours. The catalyst is recovered by filtration and the solution concentrated at 110 ° C below 1 mbar.
¹ H NMR (300 MHz, _CDCl3) / ppm: 3.75 (t, 4H); 3.54 (t, 4H); 2.82 (m, 2H); 2.63 (t, 4H); 1.78-1.45 (m, 20H); 1.42-1.23 (m, 4H); 1.16 (s, 12H); 1.10 (s, 12H); 0.89 (m, 6H). Example 11: Compound of the formula

To a solution of 90 g of benzoic acid-1-but-2-enyl-2,2,6,6-tetramethylpiperidin-4-yl ester in 200 ml of toluene are added 70 g of 4-bromo-2-butene and 100 g of potassium carbonate , The mixture is heated to 140 ° C, allowed to react for 10 hours with stirring, cooled to 20 ° C, poured into 200 ml of water and stirred. The organic layer is then collected, concentrated by removing 100 ml of solvent at 110 ° C at 20 mbar, then adding 100 ml of fresh toluene. The resulting solution is cooled to -15 ° C and added a solution of 100 g of m-chloroperbenzoic acid in 200 ml of toluene for 30 minutes with stirring. The mixture is allowed to react at 0 ° C for 2 hours, then a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. The organic layer is collected and the solvent evaporated under vacuum. The product obtained is a pale yellow liquid.
¹ H NMR (300 MHz, _CDCl3) / ppm: 7.99 (d, 2H); 7.49 (m, 1H); 7.37 (m, 2H); 5.85 (m, 1H); 5.26 (m, 1H); 5.06-5.00 (m, 2H); 4.28 (m, 1H); 1.94 (m, 2H); 1.71 (m, 2H); 1.25-1.17 (m, 15H). Example 12: Compound of the formula

To a solution of 52 g of 2,2,6,6-tetramethylpiperidine in 250 ml of hexane, 102 g of potassium carbonate and 135 g of propargyl bromide are added. The mixture is heated to 140 ° C, allowed to react for 10 hours with stirring, cooled to 20 ° C, poured into 300 ml of water and stirred. The organic layer is then collected, dried over sodium sulfate and distilled under vacuum to collect the fraction at 64 ° C and 10 mmHg, which is then dissolved in 250 ml of dichloromethane and cooled to -15 ° C. To the resulting solution, a solution of 100 g of m-chloroperbenzoic acid in 200 ml of hexane is added over 30 minutes with stirring. The mixture is allowed to react for 2 hours at 0 ° C and a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. The organic layer is collected, dried over sodium sulfate and the solvent evaporated under vacuum. The product obtained is a pale yellow liquid.
¹ H NMR (300 MHz, _CDCl3) / ppm: 6.82 (t, 1H); 5.49 (d, 2H); 1.52 (s, 6H); 1.13 (s, 12H). Example 13: Compound of the formula

A mixture of 16 g of the compound described in Example 11, 500 ml of ethanol and 0.9 g Lindlar catalyst is introduced into the autoclave. The autoclave is filled with 10 bar hydrogen and kept at 40 ° C for a period of 6 hours with stirring, then it is cooled to 20 ° C and relieved. After removal of the catalyst by filtration, the solution is concentrated under vacuum. The product obtained is obtained as a pale yellow liquid.
¹ H NMR (300 MHz, _CDCl3) / ppm: 6.29 (d, 1H); 4.01 (m, 1H); 1.57 (d, 3H); 1.45 (m, 6H); 1.12 (s, 12H). Example 14: Compound of the formula

A mixture of 38 g of the compound described in Example 11, 300 ml of toluene and 1 g of platinum supported on carbon at 5 weight percent is introduced into the autoclave. The autoclave is filled with 30 bar hydrogen and kept at 40 ° C for a period of 6 hours with stirring, then cooled to 20 ° C and relieved. After removal of the catalyst by filtration, the solvent is removed by vacuum concentration at 110 ° C and 35 mbar. The resulting product is obtained as a pale yellow liquid.
¹ H NMR (300 MHz, _CDCl3) / ppm: 3.69 (t, 2H); 1.45 (m, 8H); 1.15 (s, 12H); 0.92 (t, 3H). Example 15: Compound of the formula

207 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 100 g of DBE-2 ^O (a mixture of 75% dimethyl glutarate and 25% dimethyl adipate, available from DuPont-USA) are dissolved in toluene 500 ml, 2 g of lithium amide is added and heated and refluxed for 6 hours; while the methanol formed in the reaction is distilled off azeotropically. The mixture is then cooled to 20 ° C, washed with water, dried over sodium sulfate. The resulting solution is then reacted with allyl bromide, sodium carbonate, peracetic acid, hydrogen and 5 wt% platinum on carbon by the same procedure and in the same stoichiometric ratios described for the preparation of the compound of Example 5. The product is obtained as a pale yellow oil.
¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.63 (t, 4H); 2.24 (m, 2H); 1.86-1.71 (m, 4H-6H); 1.57-1.44 (m, 8H); 1.15 (m, 28H); 0.89 (m, 6H). Example 16: Compound of the formula

Step 1: To a solution of 64 g of 2,4,6-tris (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl)) - 1,3,5-triazine in 300 ml Toluene is added to 48 g of allyl bromide and 55.8 g of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours, cooled to 60 ° C and 300 ml of water are added with stirring. The organic layer is then collected, concentrated by removing 100 ml of solvent at 110 ° C at 20 mbar, added to 400 ml of fresh toluene, cooled to -5 ° C and 57 g of a solution of 39 wt .-% - peracetic acid in acetic acid added with stirring within 30 minutes. The temperature is allowed to rise to 0 ° C and the reaction mixture is allowed to react for 2 hours. A solution from 80 g of sodium carbonate in 500 ml of water is added and kept at 0 ° C for 30 minutes with stirring. The organic layer is collected and dried over sodium sulfate.

Step 2: The solution is introduced into a 1 liter stainless steel autoclave. After adding 2 g of platinum, supported on carbon, with 5 weight percent, the autoclave is filled with 40 bar of hydrogen and kept at 70 ° C with stirring for a period of 6 hours, then cooled to 20 ° C and vented. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. The product is obtained as a white solid, mp 92-100 ° C. Example 17: Compound of the formula

The solution obtained in Step 1 of Example 14 is added with 43 g of bromine within 30 minutes with stirring at 25 ° C in the dark. The mixture is allowed to react for 6 hours at 25 ° C, washed with a solution of 54 g of potassium carbonate in 500 ml of water, collected, dried with sodium sulfate and concentrated at 100 ° C under reduced pressure (10 mbar). The resulting, pale pink solid has a melting point of 106-110 ° C. Example 18: Compound of the formula

To the solution obtained in Step 1 of Example 2, 88 g of bromine are added over 30 minutes with stirring at 25 ° C in the dark. The mixture is allowed to react for 6 hours at 25 ° C, washed with a solution of 108 g of potassium carbonate in 1000 ml of water, collected, dried with sodium sulfate and concentrated at 120 ° C under reduced pressure (10 mbar). The resulting, pale yellow solid has a melting point higher than 250 ° C (decomposition).
Bromine content: 32.1 weight percent; Mn (according to GPC): 2862.

applications

Example 20: LIGHT STABILIZATION EFFECT IN PP TAPES

1 g of each compound of the list below, 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 0.5 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1 g of calcium stearate are in a turbomixer with 1000 g of polypropylene powder having a melt index of 2.1 g / 10 min (measured at 230 ° C and 2.16 kg), which already 1 g of tris (2,4-di-tert butylphenyl phosphite) and 10.5 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate).

The mixture is extruded at 200-220 ° C into polymer granules, which are then processed into 50 μm thick and 2.5 mm wide drawn strips using a semi-industrial device (Leonard-Sumirago (VA) -Italy) and under the following conditions : Extruder temperature: 210-230 ° C Head temperature: 240-260 ° C draw ratio: 1: 6

The tapes thus prepared are mounted on a white board and exposed in a Weather-O-Meter 65 WR (ASTM G26 96D 2565-85) with a black panel temperature of 63 ° C.

The residual strength is measured by means of a constant velocity extensometer on a sample taken after different exposure times; from this, the exposure time (in hours) required to halve the initial strength (T50) is calculated.

For comparison, tapes prepared under the same conditions as described above but without the addition of the stabilizers of the present invention are exposed.

The results obtained are shown in the table below. Invention compound T50 (hours) Nothing 340 Compound of Example 5 3040

Example 21: LIGHT STABILIZATION EFFECT IN LDPE FOILS

Each compound of the list following is a masterbatch with LDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy), characterized by a density of 0.921 g / cm ³ and a melt flow index (190 ° C / 2.16 kg ) of 0.60 g / 10 minutes, mixed in a slow speed mixer. The masterbatch was previously prepared by extruding powdered LDPE and 10% by weight of the compounds listed below.

The mixture is blow-extruded at 210 ° C and films with a thickness of 150 microns are obtained.

The films are mounted in metal frames on a white board and exposed in an Atlas xenon arc Weather-O-Meter Ci 65 at a black panel temperature of 63 ° C, continuous dry cycle, according to ASTM G 26-96.

During the exposure, the properties are evaluated from time to time by measuring the carbonyl increment (iCO) of an FT-IR spectrophotometer and checking the samples for embrittlement. For some samples, the residual tensile strength is measured with a constant rate extensometer on samples taken after different exposure times; from this, the exposure time required to halve the initial tensile strength (T50) is calculated.

The results are shown in the table below; a small increase in carbonyl concentration and a high T50 time show good stabilization. Table: Increase in carbonyl concentration (iCO) after 4760 hours exposure and T50 connection T50 / hour iCO 0.2% of Example 2 > 7050 0.08 without stabilizer 660 Embrittlement after 1560 h

Example 22: LIGHT STABILIZATION EFFECT IN LDPE FOILS TREATED WITH BORDEAUX MIXTURE

Each compound of the list following is a masterbatch with LDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy), characterized by a density of 0.921 g / cm ³ and a melt flow index (190 ° C / 2.16 kg ) of 0.60 g / 10 minutes, mixed in a slow speed mixer.

The masterbatch was previously prepared by extruding powdered LDPE and 10% by weight of the compound listed below.

The mixture is blow-extruded at 210 ° C and films with a thickness of 150 microns are obtained.

Sheets for pesticide treatment are kept for 24 hours in a suspension of Bordeaux mixture (widely used pesticide based on copper sulphate) and water (10 g mixture in 1 liter of water).

The treated films are placed in quartz tubes and exposed in an Atlas xenon arc Weather-O-Meter Ci 65 at a black panel temperature of 63 ° C, continuous dry cycle, according to ASTM G 26-96. During exposure, the properties are evaluated from time to time by measuring the carbonyl increment (increase in carbonyl concentration; iCO) with an FT-IR spectrophotometer. The results are shown in the table below. Table: Increase in carbonyl concentration (iCO) after designated hours of weathering connection iCO after 0 hours 0.15% Example 2 0 without stabilizer 0

Example 23: LIGHT STABILIZATION EFFECT IN LDPE FOILS TREATED WITH VAPAM

Each compound of the list following is a masterbatch with LDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy), characterized by a density of 0.921 g / cm ³ and a melt flow index (190 ° C / 2.16 kg ) of 0.60 g / 10 minutes, mixed in a slow speed mixer.

The masterbatch was previously prepared by extruding powdered LDPE and 10% by weight of the compound listed below.

The mixture is blow-extruded at 210 ° C and films with a thickness of 150 microns are obtained.

Pesticide treatment films are held in a dryer for 20 days at 30 ° C in the presence of the vapors emitted from 2 liters of aqueous solution containing 50% VAPAM (Basilini S.p.A., Treviglio / BG, Italy) Again, an aqueous solution of 382 g per liter of metam sodium of the formula CH ₃ -NH-CS-SNa.

The treated films are placed in quartz tubes and exposed in an Atlas xenon arc Weather-O-Meter Ci 65 at a black panel temperature of 63 ° C, continuous dry cycle, according to ASTM G 26-96.

During exposure, the properties are evaluated from time to time by measuring the carbonyl increment with an FT-IR spectrophotometer and testing the samples for embrittlement. The results are shown in the table below; a slight increase in carbonyl concentration indicates good stabilization. Table: Increase in carbonyl concentration (iCO) after 1000 hours of exposure connection concentration iCO Example 2 0.2% 0.38 without stabilizer 0 embrittlement

Example 24: LIGHT STABILIZATION EFFECT OF GREENHOUSE FILMS

Each compound of the list following is a masterbatch with LDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy), characterized by a density of 0.921 g / cm ³ and a melt flow index (190 ° C / 2.16 kg ) of 0.60 g / 10 minutes, mixed in a slow speed mixer.

The masterbatch was prepared beforehand by extruding powdered LDPE and 10% by weight of the hindered hydroxylamine ether of the present invention (Compound A) and the respective concentrations of Component B (= Oxo and / or Hydroxyl Group containing metal stabilizer) and C (another co-stabilizer salt of a carboxylic acid ) produced.

The mixture is blow-extruded at 210 ° C and films with a thickness of 150 microns are obtained. The slides are illuminated on the southern roof surface of a greenhouse in Pontecchio Marconi (Bologna-Italy). The following pesticides are used in the greenhouse:
VAPAM (Basilini S.p.A., Treviglio / BG, Italy.), Which itself is an aqueous solution of 382 g per liter of metam-sodium having the formula CH ₃ -NH-CS-SNa;
SESMETRIN (Bimex S.p.A., Isola / VI, Italy), namely a 23.75% (% w / w) aqueous solution of permethrin of the formula

The greenhouse is treated with a solution of 4 liters of VAPAM in 10 liters of water every 6 months and with SESMETRIN (5 g in 5 liters of water) every month.

During exposure, the performance is evaluated from time to time by measuring the carbonyl increment with an FT-IR spectrophotometer. Exposure is measured in Kilolangley (Kly; energy per unit area); 1100 Kly correspond to 1 year exposure. Connection A Component B calcium stearate iCO after 0.4% Example 2 0.2% ZnO 0.2 0.4% Example 2 0 0 Nothing 0 0

Example 25: Wood coating

a) Impregnation

The substrate (pine) is impregnated with a commercially available impregnation ("Xylamon ^® Incolore" solids content 5.2% from Sepam).

The impregnation is applied with a brush (1 application) and dried for 24 hours at room temperature.

b) cover layer:

A cover layer is made of:
73.8 parts of alkyd resin (Jagol PS 21 ^®, E. Hunter KG)
0.52 parts of an anti-skinning agent (Exkin ^® 2, Servo Delden BV),
20.8 parts of aliphatic hydrocarbon solvent (Exxsol D 40 ^®, German Exxon Chemical GmbH)
4.16 parts metal dryer (Jäger Antihydro-Dryer ^® , E. Jäger KG),
0.70 parts of a PE wax, 21% in solvent (Lanco GLIDD AH ^®, GM Langer & Co).

UV-Absorptionsmittel von Ciba Specialty Chemicals) und 1% Stabilisator gemäß der Erfindung, wie in der nachstehenden Tabelle ausgewiesen.The cover layer is stabilized with 2% UVA (compound of formula

UV absorber from Ciba Specialty Chemicals) and 1% stabilizer according to the invention as shown in the table below.

All concentrations are based on the weight of the binder solids.

The topcoat is applied to the impregnated pine panels by brushing (2 applications) and dried for 24 hours at room temperature after each application.

The panels are subjected to accelerated weathering: (QUV, 8 hours light at 70 ° C, 4 hours condensation at 50 ° C, UV-A lamps).

Gloss (60 °) is measured according to DIN 67530 every 400 hours of weathering. An unexposed pine wood panel with a non-stabilized cover layer is used as a cover.

The results are shown in the table below. Table: Gloss (60 °) after 2400 hours of exposure Unstabilized topcoat 25 2% UVA 63 2% UVA + 1% compound of Example 5 86 Initial gloss (60 °) for all samples: 92-93

The results show that a good gloss retention is achieved with the stabilizer according to the invention.

Example 26 Stabilization of a 2-Layer Metallic Varnish

Test light stabilizers are dissolved in 30 g of Solvesso ^® 100 tested in a clearcoat having the following composition (parts by weight): Synthacryl ^® SC 303 ¹⁾ 27.51 Synthacryl ^® SC 370 ²⁾ 23.34 Maprenal ^® 650 ³⁾ 27.29 Butyl acetate / butanol (37/8) 4.33 isobutanol 4.87 Solvess ^® 150 ⁴⁾ 2.72 Crystal Oil K-30 ^{5 )} 8.74 Leveling aid Baysilon ^® MA ^{6 )} 1.20 100.00 ¹ acrylate resin, ^® Hoechst AG; 65% solution in xylene / butanol (26: 9)
² acrylate resin, ^® Hoechst AG; 75% solution in Solvesso ^® 100 ^4
3 melamine resin, ^® Hoechst AG; 55% solution in isobutanol
⁴ mixture of aromatic hydrocarbons, boiling range: 182-203 ° C (Solvesso ^® 150) or 161-178 ° C (Solvesso ^® 100); Manufacturer: ^® Esso
⁵ Mixture of aliphatic hydrocarbons, boiling range: 145-200 ° C; Manufacturer: ^® Shell
⁶ 1% in Solvesso ^® 150; Manufacturer: ^® Bayer AG

1% of the stabilizer listed in the table below and 1.5% of the UV A of Example 25 are added to the clear coat based on the solids content of the paint. For comparison, a clear coat containing no light stabilizers is used.

The clearcoat is diluted with Solvesso ^® 100 to spray viscosity and is applied by spraying to a prepared aluminum panel ^(® Uniprime Epoxy, silver metallic basecoat) which is baked at a temperature of 130 ° C for 30 minutes to a dry film thickness of 40-50 microns Clearcoat ,

The samples are then weathered in a Weather-O-Meter Xe-Wom by Atlas (CAM 180) in the following cycle: 40 minutes UV light, 20 minutes light with rain (from the front), 60 minutes light, 60 minutes dark with rain (both sides), light at 70 ° C, darkness at 40 ° C (filter: quartz / boron, 0.55 W / cm ² at 340 nm).

The surface gloss (20 ° gloss, defined in DIN 67530) of the samples is then measured at regular intervals; high values indicate good stabilization. The results are shown in the table below. Table: light stabilizer 20 ° gloss (DIN 67530) after ... hours of weathering 0 hours 800 hours 3200 hours Nothing 94 33 Cracking after 800 hours 1% compound of Example 5 + 1.5% UVA 92 92 72

• 1. Verfahren zur Herstellung einer Verbindung der Formel I
  
  worin R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen; R₅, R₆, R₇, R₈ und R₉ unabhängig voneinander H, C₁-C₈-Alkyl, C₂-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen und R₇ und R₈ zusammen ebenfalls eine chemische Bindung bilden können; und R eine organische verbindende Gruppe, die 2-500 Kohlenstoffatome enthält, darstellt und zusammen mit den Kohlenstoffatomen, an die sie direkt gebunden ist, und dem Stickstoffatom eine substituierte 5-, 6- oder 7-gliedrige, cyclische Ringstruktur bildet; dadurch gekennzeichnet, daß eine Verbindung der Formel II
  
  worin alle Reste R und R₁–R₉ wie in Formel I definiert sind, oxidiert wird.
• 2. Verfahren nach Anspruch 1, wobei die Oxidationsreaktion in Anwesenheit eines Lösungsmittels und eines Oxidationsmittels, ausgewählt aus Sauerstoff, Peroxiden, Nitraten, Permanganaten, Chloraten, ausgeführt wird.
• 3. Verfahren nach Anspruch 1 zur Herstellung einer Verbindung der Formel I durch Oxidation einer Verbindung der Formel II, worin R₁, R₂, R₃ und R₄ unabhängig voneinander C₁-C₈-Alkyl oder C₁-C₅-Hydroxyalkyl darstellen oder R₁ und R₂ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen oder R₃ und R₄ zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, C₅-C₁₂-Cycloalkyl darstellen; R₅, R₆, R₇, R₈ und R₉ unabhängig voneinander H, C₁-C₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₁₂-Aryl, eine Elektronen-anziehende Gruppe, C₆-C₁₂-Aryl, das mit C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen und R einen C₃-C₅₀₀-Kohlenwasserstoffrest, der gegebenenfalls 1-200 Heteroatome, ausgewählt aus Stickstoff, Sauerstoff, Phosphor, Schwefel und Halogen enthält, darstellt und zusammen mit den zwei Kohlenstoffatomen und dem Stickstoffatom eine substituierte 6-gliedrige, cyclische Ringstruktur bildet.
• 4. Verfahren nach Anspruch 1, wobei in den Verbindungen der Formeln I und II R₁, R₂, R₃ und R₄ unabhängig vorzugsweise Methyl oder Ethyl darstellen, R₅ und R₆ unabhängig H oder Methyl darstellen und R₇, R₈ und R₉ unabhängig C₁-C₄-Halogenalkyl, Phenyl, Vinyl, Nitro, CN, COOR₁₀ darstellen oder R₇ und R₈ zusammen eine chemische Bindung bilden und die verbindende Gruppe R einen C₂-C₅₀₀-Kohlenwasserstoffrest oder einen C₂-C₅₀₀-Kohlenwasserstoffrest, der 1-200 Heteroatome, ausgewählt aus Stickstoff, Sauerstoff, Phosphor, Schwefel, Silicium und Halogen, enthält, darstellt.
• 5. Verfahren zur Herstellung einer Verbindung der Formel Va
  
  worin R, R₁, R₂, R₃ und R₄, R₅, R₆ und R₉ wie in Anspruch 1 für Formel I definiert sind, R₇ und R₈ H, C₁-C₈-Alkyl, C₃-C₈-Alkenyl, C₅-C₁₂-Aryl, C₁-C₄-Halogenalkyl, Halogen, eine Elektronen-anziehende Gruppe oder C₆-C₁₂-Aryl, das mit einem Rest, ausgewählt aus C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, substituiert ist, darstellen; und beide Reste R₂₀ und R₂₁ entweder Wasserstoff oder Halogen darstellen, dadurch gekennzeichnet, daß eine Verbindung der wie in Anspruch 1 beschriebenen Formel II oxidiert wird und das erhaltene Zwischenprodukt der Formel I Hydrierung und/oder Halogenierung unterzogen wird.

In order to safeguard the origin disclosure, the following representation of the claims originally filed in the parent application is as follows:

• 1. A process for the preparation of a compound of the formula I.
  
  in which R ₁ , R ₂ , R ₃ and R _4, independently of one another, are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ - C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, and R ₇ and R ₈ together can also form a chemical bond; and R represents an organic linking group containing 2-500 carbon atoms and together with the carbon atoms to which it is directly attached and the nitrogen atom forms a substituted 5-, 6- or 7-membered cyclic ring structure; characterized in that a compound of the formula II
  
  wherein all of R and R ₁ -R _{9 are} as defined in formula I is oxidized.
• A process according to claim 1, wherein the oxidation reaction is carried out in the presence of a solvent and an oxidizing agent selected from oxygen, peroxides, nitrates, permanganates, chlorates.
• 3. The method of claim 1 for the preparation of a compound of formula I by oxidation of a compound of formula II, wherein R ₁ , R ₂ , R ₃ and R _{4 are} independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ cycloalkyl group; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, an electron-withdrawing group, C ₆ -C ₁₂ -aryl substituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, and R is a C ₃ -C ₅₀₀ -hydrocarbon radical, optionally containing from 1 to 400 heteroatoms selected from Nitrogen, oxygen, phosphorus, sulfur and halogen, and together with the two carbon atoms and the nitrogen atom form a substituted 6-membered cyclic ring structure.
• 4. The method of claim 1, wherein in the compounds of formulas I and II R ₁ , R ₂ , R ₃ and R _{4 are} independently preferably methyl or ethyl, R ₅ and R _{6 are} independently H or methyl and R ₇ , R ₈ and R _{9 are} independently C ₁ -C ₄ haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ , or R ₇ and R ₈ together form a chemical bond and the linking group R is a C ₂ -C ₅₀₀ hydrocarbon radical or a C C ₂ -C ₅₀₀ hydrocarbon radical containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen.
• 5. Process for the preparation of a compound of formula Va
  
  wherein R, R ₁ , R ₂ , R ₃ and R ₄ , R ₅ , R ₆ and R _{9 are} as defined in claim 1 for formula I, R ₇ and R _{8 are} H, C ₁ -C ₈ alkyl, C ₃ C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, halogen, an electron attractive group or C ₆ -C ₁₂ aryl, with a radical selected from C ₁ -C ₄ Alkyl, C ₁ -C ₄ alkoxy, halogen, is substituted; and both R ₂₀ and R _{21 are} either hydrogen or halogen, characterized in that a compound of formula II as described in claim 1 is oxidized and the resulting intermediate of formula I is subjected to hydrogenation and / or halogenation.

Claims (13)

A composition comprising A) an organic polymer sensitive to oxidative degradation, thermal degradation and / or degradation by actinic radiation, and B) at least one compound of formulas IIIa, IVa or Va

wherein R 'and R each represents an organic linking group of the formula

group; E _{2 is} -CO- or - (CH ₂ ) _p - wherein p is 0, 1 or 2; E _{1 represents} a carbon atom which carries the two radicals R ₂₄ and R ₂₅ , or> NR ₂₅ or is oxygen and R ₂₄ and R _{25 represent} hydrogen or an organic radical, characterized in that the linking group R is a total of 2 Contains 500 carbon atoms; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; R ₂₀ and R _{21 are} halogen and R ₂₂ and R _{23 are} hydrogen or together represent a chemical bond. A composition according to claim 1, comprising as organic polymer a thermoplastic organic polymer or a binder for a coating. A composition according to claim 1, comprising from 0.1 to 10% by weight of the stabilizer of component B, based on the material to be stabilized. A composition according to claim 1 comprising another component selected from solvents, pigments, dyes, plasticizers, antioxidants, stabilizers, thixotropic agents, leveling agents, other light stabilizers, metal passivators, phosphites, phosphonites and flame retardants. A composition according to claim 4, comprising as further component a UV absorber selected from the 2-hydroxyphenylbenzotriazoles, the 2-hydroxyphenyl-s-triazines, the benzophenones. Compound of formula Ia

wherein the index n ranges from 1 to 15; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are C ₁ -C ₈ -alkyl, C ₃ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, an electron-withdrawing group, C ₆ -C ₁₂ -aryl substituted with C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen; R _{12 is} C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkenylene, C ₅ -C ₇ -cycloalkylene, C ₅ -C ₇ -cycloalkylenedi (C ₁ -C ₄ -alkylene), C ₁ -C ₄ -alkylenedi (C ₅ -C ₇ -cycloalkylene), phenylenedio (C ₁ -C ₄ -alkylene) or C ₄ -C ₁₂ -alkylene interrupted by 1,4-piperazinediyl, -O- or> NX ₁ , where X _{1 is} C ₁ C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or has one of the definitions given below for R ₁₄ , with the exception of hydrogen, or R _{12 represents} a group of the formula (Ib ') or (Ic') .

X _{2 is} C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl, phenyl which is unsubstituted or with 1, 2 or 3 C ₁ C ₄ alkyl or C ₁ -C ₄ alkoxy substituted; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ -alkyl, and the radicals X ₃ independently of one another represent C ₂ -C ₁₂ -alkylene; each A independently represents -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of formula (Id ');

R ₁₃ , R ₁₄ and R ₁₅ , which are the same or different, are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl is; C ₃ -C ₁₈ alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or C ₂ -C ₄ -alkyl which is in the 2-, 3- or 4-position with -OH, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of the formula ( Ie ') is substituted,

wherein Y represents -O-, -CH ₂ -, -CH ₂ CH ₂ - or> N-CH ₃ , or -N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie '); X represents -O- or> NR ₁₆ ; R _{16 is} hydrogen, C ₁ -C ₁₈ -alkyl, C ₃ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (If ')

or C ₂ -C ₄ -alkyl substituted with -OH in the 2, 3 or 4 position, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of Represents formula (Ie '); R _{11 has} one of the definitions given for R ₁₆ and the radicals B independently of one another have one of the definitions given for A. Compound of formula IIIc, IVa or Va

wherein R is an organic linking group of the formula

represents; E _{2 is} -CO- or - (CH ₂ ) _p - wherein p is 0, 1 or 2; E _{1 represents} a carbon atom bearing two radicals R ₂₄ and R ₂₅ , or> NR ₂₅ or oxygen and R ₂₄ and R _{25 represent} hydrogen or an organic radical, characterized in that the linking group R is a total of 2-500 Containing carbon atoms and together with the carbon atoms connected directly to it and the nitrogen atom form a substituted, 5-, 6- or 7-membered cyclic ring structure; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₅ -C ₁₂ -aryl, C ₁ -C ₄ -haloalkyl, an electron attracting group or C ₆ -C ₁₂ aryl substituted with a radical selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; R ₂₀ and R _{21 are} halogen and R ₂₂ and R _{23 are} hydrogen or together represent a chemical bond, with the proviso that R in formula IIIc is not the linking group

wherein R ₂₄ and R ₂₅ together represent = O, or wherein R _{24 represents} hydrogen and R _{25 represents} hydrogen, OH or alkanoyloxy substituted with phenoxy, alkylphenoxy, phenyl or alkylphenyl. A compound according to claim 7, wherein R represents a divalent C ₇ -C ₅₀₀ hydrocarbon radical or a C ₂ -C ₅₀₀ hydrocarbon radical containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen, and with the structure

where p is 0, 1 or 2; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl, or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ - C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; R ₅ and R ₆ independently of one another represent H or methyl and R ₇ , R ₈ and R ₉ independently of one another are C ₁ -C ₄ -haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ , in which R _{10 is} C ₁ -C ₁₂ - Alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl; R ₂₄ and R ₂₅ independently of one another represent hydrogen or an organic radical as defined in claim 12 and R _{26 represents} hydrogen or an organic radical which together with the remaining structure of formula (VIb) forms a C ₂ -C ₅₀₀ -hydrocarbon radical, which contains 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen. A compound according to claim 7, corresponding to the formulas (1a), (1b) or (2a) or containing at least one group of the formula (3) or (4)

wherein n _{1 is} a number from 1 to 4, G and G ₁ independently of one another represent hydrogen or methyl, G ₁₁ n-propoxy, O-CH = C =CH ₂ , O-CH =CH-CH ₃ or halogenated n-propoxy, in particular n-propoxy or brominated n-propoxy; G ₁₂ when n _{1 is} 1, C ₁ -C ₁₈ alkyl not interrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms or of an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms, each carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety, if present, with 1 to 3 groups -COOZ ₁₂ , wherein Z ₁₂ H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₂ -alkenyl, C ₅ -C ₇ -cycloalkyl, Phenyl or benzyl, may be substituted; G ₁₂ , when n _{1 is} 2, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical , preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms or of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, wherein each dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety may be substituted with one or two groups -COOZ ₁₂ ; G ₁₂ , when n is ₁ , represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety with -COOZ ₁₂ , of an aromatic tricarbamic acid or a phosphorus-containing acid, or a trivalent silyl group and G ₁₂ when n is _{1 represents} a tetravalent residue of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are C ₁ -C ₈ -alkyl or C ₁ -C ₅ -hydroxyalkyl or R ₁ and R ₂ together with the carbon atom to which they are attached are C ₅ -C ₁₂ -cycloalkyl or R ₃ and R ₄ together with the carbon atom to which they are attached represent C ₅ -C ₁₂ -cycloalkyl; G represents hydrogen or methyl; G ₁ and G _{2 are} independently hydrogen, methyl, or together represent a substituent = O; and G _{3 is} a direct bond or methylene, open bonds of formulas (3) and (4) are attached to a carbon, nitrogen or oxygen atom of an organic radical as defined above, G _{13 is} hydrogen, C ₁ -C ₁₂ alkyl , C ₂ -C ₅ -hydroxyalkyl, C ₅ -C ₇ -cycloalkyl, C ₇ -C ₈ -aralkyl, C ₁ -C ₁₈ -alkanoyl, C ₃ -C ₅ -alkenoyl, benzoyl or a group of the formula (1b- 1)

represents, n _{2 is} the number 1, 2 or 3; and G ₁₄ , when n is ₂ , is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, C ₁ -C ₄ alkyl which is hydroxyl, Cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CH ₂ -CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; G ₁₄ , when n _{2 is} 2, C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, a group -CH ₂ -CH (OH) -CH ₂ or a group -CH ₂ -CH (OH ) -CH ₂ -ODO-, wherein DC is C ₂ -C ₁₀ -alkylene, C ₆ -CF ₅ -arylene, C ₆ -C ₁₂ -cycloalkylene, or, provided that G _{13 is} not alkanoyl, alkenoyl or Benzoyl, G _{14 is} alternatively 1-oxo-C ₂ -C ₁₂ alkylene, a bivalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group -CO- may represent, G ₁₄ , when n is ₂ 3, a group

or when n is ₂ , G ₁₃ and G ₁₄ together may be a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid. A compound according to claim 7 of formula IIIb

in which the radicals A are, independently of one another, -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of the formula (IIId)

group; X is -O- or> NR ₁₆ , R _{16 is} hydrogen, C ₁ -C ₁₈ -alkyl, C ₃ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ - C ₄ alkyl is substituted; C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (IIIf)

or C ₂ -C ₄ -alkyl which is in the 2, 3 or 4 position with -OH, C ₁ -C ₈ -alkoxy, di (C ₁ -C ₄ -alkyl) amino or a group of the formula ( Ie ') is substituted; R _{11 has} one of the definitions given for R ₁₆ and the radicals B independently of one another have one of the definitions given for A and in which formula (Ie ') and all other symbols are as defined for formula Ia in claim 11. Use of a compound of the formula Ia according to Claim 6 and / or of the formula IIIc, IVa, Va according to Claim 7 as stabilizer for organic material against degradation by light, oxygen and / or heat. A method for stabilizing an organic material against degradation by light, oxygen and / or heat by applying a stabilizer to the material or incorporating a stabilizer in the material, characterized in that the stabilizer is a compound of formula Ia according to claim 6 and / or the formula IIIc, IVa or Va according to claim 7. Use of a compound of formula IIIc or Va according to claim 7 as a flame retardant for an organic polymer.