NL1011394C2 - Preparation of sterically hindered amine ethers. - Google Patents

Description

i

Preparation of sterically hindered amine ethers

The invention relates to a new process for the preparation of sterically hindered amine ethers, to new compounds of this class, to their use as stabilizers for organic material against the degradation by light, oxygen and / or heat and to corresponding compositions .

A number of publications describe the stabilization of organic matter using specific sterically hindered amine compounds (HALS) 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 contains an additional organic substituent bonded via an oxygen atom (NOR-HALS; Kurumada et al., J. Polym. Sci., Poly. Chem. Ed. 22, 277-81 (1984); US-A-5204473); the oxygen-bound substituent is introduced into this compound by etherification of the free oxyl or hydroxylamine with suitable agents.

Some N-allyl nitroxides are rearranged to amine ethers under certain conditions (Meisenheimer rearrangement; Chem. Ber. 52, 1667 (1919);

Chem. Ber. 55, 513 (1922)). Cleavage of the nitroxide with the formation of olefin and hydroxylamine (Cope elimination) is a competitive reaction, the rate of which increases with increasing steric hindrance (J. March, Advanced Organic Chemistry, IV Ed., Wiley, 1992).

It has now surprisingly been found that the oxidation of a 1-allyl-substituted, sterically hindered amine effectively leads to the corresponding 1-allyloxy-substituted product. The invention therefore relates to a process for the preparation of a compound of the formula I.

R1 \ .R2 X Re yRa

<N-O - L- <O

V R Re 30 / \ R9 where 10 1 1394 2

R 1 R 2, R 1 and R 4 independently of one another are C 1 -C 5 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 1 and R 4 together with the carbon atom to which they are attached C5 -C12 cycloalkyl; 5 R 5, R 6, R 7, R 8 and R <, independently of one another H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 12 aryl, C 1 -C 4 haloalkyl, an electron withdrawing group or C6-C 2 aryl which is substituted with a radical selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; and R7 and Rg together can also form a chemical bond; and R is an organic linking group containing 2-500 carbon atoms and together with the carbon atoms to which it is directly bonded and the nitrogen atom forms a substituted 5, 6 or 7-membered cyclic ring structure; wherein R is preferably a C2-CS00 hydrocarbon group optionally containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen, and characterized in that a compound of the formula II is 15 r / r *

Rs 11 / R8 V-P% (11) r3A4 R "wherein all radicals R and R 1 -R 9 are as defined for formula I are oxidized.

R7 and Rg together as a chemical bond form an allenic 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 independently of one another are preferably methyl or ethyl, especially methyl.

R 5 * 6 * R 7, R 8 and R, as an electron withdrawing group, include -CN, nitro, halogen or -COOR) O, where R 10 is C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl 30 or phenyl. -CN or -COOR10, where R10 is C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl or phenyl, especially wherein R 10 is C 1 -C 12 alkyl or cyclohexyl, are preferred electron-withdrawing group.

Preferably R5, R6, R7, Rg and R9 independently of one another are H or methyl, in particular 1011334 »3. Also preferred are compounds wherein R5 and R6 are independently of one another H or methyl, especially H, and R7, R8 and R, independently of each other, are haloalkyl, phenyl, vinyl, nitro, CN, COOR, O or R7 and Rg together form a chemical bond.

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

Of particular interest is a process for the preparation of a compound of the formula I by oxidation of a compound of the formula II, wherein R 1, R 2, R 3 and R 4 independently of one another are C 1 -C 6 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 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C 5 -C 1 2 cycloalkyl; R5, R6, R7, Rg and R, independently of one another H, C 1 -C 8 alkyl, C3-Cg alkenyl, C5-Cl 2 aryl, an electron withdrawing group or C6-C 2 aryl substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; and R is a C3-C500 hydrocarbon group optionally containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, which together with the two carbon atoms and the nitrogen atom forms a substituted 6-membered cyclic ring structure.

Aryl is a group that complies with Debye-Hückel's law; phenyl and naphthyl are preferred as C6-C12 aryl.

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 bonded through a carbonyl bond; thus C2-C20alkanoyl includes acetyl, propionyl, butyryl, hexanoyl, stearoyl.

Haloalkyl is alkyl substituted with halo, e.g. with 1 or 2 halogen atoms. Halogen atoms are preferably chlorine or bromine, in particular bromine.

Cycloalkyl is a saturated honorable monocyclic hydrocarbon radical, such as e.g. cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl; cyclohexyl is preferred.

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 characteristic functional groups such as oxo, oxa, hydroxy, carboxy, ester, amino, amido, nitro, nitrilo, isocyanate, fluorine, chlorine, bromine, phosphate, phosphonate, phosphite, silyl, thio, sulfide, sulfinyl, sulfo, heterocyclyl including pyrrolyl, indyl, carbazolyl, furyl, benzofuryl, thiophenyl, benzothiophenyl, pyridyl, quinolyl, isoquininyl, pyridyl pyrazinyl, triazolyl, benzotriazolyl, triazinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and the corresponding saturated and / or substituted groups such as, for example, piperidyl, piperazinyl, morpholinyl, etc. They may be interrupted by one or more of these groups; usually no O-O, O-N bonds (except nitro, cyanate, isocyanate, nitroso), N-N (except in heterocyclic ring structures), N-P or P-P are present in any order .

Preferably, in organic radicals or hydrocarbons containing heteroatoms, such as R, no more than one heteroatom is bonded to the same carbon atom via a single bond. An intermediate piece, which consists of one or more heteroatoms, is usually embedded in a carbon chain or ring or inserted in a carbon-hydrogen bond.

Compounds of the formula I can be monomers or polymers. They contain 1 or more groups with the formula Γ 25 R 1 \ β2

—V R8 V7 / RS

Vo - <r) 30 3

In case the compounds of the formula Γ are polymers, they contain a group of the formula Γ in the repeating structural unit.

1011334 * 5

Starting compounds of the formula II are known in the art or can be obtained analogously to known compounds. The present process can start with isolated compounds of the formula II or the solution of these starting compounds obtained immediately after the synthesis can be used.

In the method of the present invention, the oxidation reaction can be carried out using known oxidants, such as e.g. oxygen, peroxides or other oxidizing agents such as nitrates, permanganates, chlorates; the peroxides, such as hydrogen peroxide based systems, especially peracids such as perbenzoic acid or peracetic acid, are preferred. The oxidant is usually used in a stoichiometric amount or in an excess, e.g. 1-2 moles of active oxygen atoms for each group of the formula Γ in the desired product are used.

The reaction can be carried out in the presence of a suitable solvent, such as, 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, dichloromethane; a C 1 -C 4 alcohol, benzene, toluene, xylene or a chlorinated C 1 -C 6 hydrocarbon are preferred.

The temperature and pressure are not critical and depend mainly on the oxidant system used; preferably, the temperature during the reaction is kept in the range from -20 ° C to + 40 ° C. Usually the pressure is kept near atmospheric pressure, e.g. between 0.5 and 1.5 bar; if the oxidation is carried out with gaseous oxygen, the pressure of the oxygen or oxygen / inert gas may exceed atmospheric pressure.

The method of the present invention can be followed by other process steps known in the art, such as e.g. hydrogenation of an ethylenic double bond, halogenation, e.g. bromination, of an ethylenic double bond and / or polymerization, with or without pre-isolation of the product of the formula I.

Hydrogenation of the ethylenic double bond (carbon-carbon double bond) in the compound of formula I can be accomplished by methods known in the art, such as e.g. reaction with gaseous hydrogen 6 under catalytic conditions or reaction with hydrogenating agents. Catalytic hydrogenation is preferred; known catalysts such as Pt, Pd,

Ni, Ru, Rh, or a support such as carbon or unsupported, Raney-Ni etc. are used.

The hydrogenation of an allenic double bond in a compound of the formula I wherein R7 and Rg together are a chemical bond proceeds in 2 steps.

The first step leads to a partially hydrogenated product, which can be isolated or subjected to further derivatization and corresponding to formula IV

RY2 D ^ V, ^ H / Rs V \ (| V> R9 R6 R 3 R 4 15 where R, R, -R6 and R9 are as defined above.

Complete hydrogenation gives a product of the formula III

20 V / r 2 X R »H / R = r; n-o - C-c (III)

x TH

R 3 R 4 where R, R, -R 6 and R 9 are as defined above in formula I and R 7 and R 9 H, C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 5 -C 2 aryl, C, -C 4 haloalkyl, an electron withdrawing group or C6 -C12 aryl which is substituted with a moiety selected from C1 -C4 alkyl, C1 -C4 alkoxy, halogen.

Halogenation is another tracking reaction that can be carried out after the method of the present invention essentially according to the methods known in the art and using the appropriate reagent, such as e.g. is summarized in J. March, Advanced Organic Chemistry: Reaction 10 '; ;: c: 7 mechanisms and Structure, fourth edition, Wiley, 1992, biz. 812. Thereby, halogen is added to the carbon-carbon double bond of a compound of the formula I or OV, resulting in an α, β-dihalogenated product. The halogen reagent X2, wherein X is F, Cl, Br, I or preferably Cl or Br, especially 5 Br, can be used in gaseous, liquid or solid form, pure or as a solution. Halogen can also be released in appropriate amounts during the reaction using a suitable carrier or source.

The reactions can be carried out according to methods known in the art, whereby hydrogen pressures in the usual range, preferably between 0.5 and about 200 bar, in particular between 1 and 100 bar (1 bar = 105 Pa) are used. The reactions can be carried out using suitable solvents, e.g. water, hydrocarbons such as hexane, petroleum 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 generally range from -10 ° C to about 150 ° C, e.g. between 0 ° C and the boiling point of the solvent as in the range of 0-100 ° C or 20-80 ° C.

The present invention therefore also relates to a process * for the preparation of a compound of the formula V.

20 R '\ XR2 V R. R7 R5 N — O ---- R 6 (V) R 9 ^ 20 ^ 21 R3X R 4 25 3 where R, R, R2, R3 and R4, Rs, R6 and R, as defined in the formula I, R7 and Rg are H, C, -C 8 alkyl, C3-C 8 alkenyl, C 5 -C | 2 aryl, C, -C 4 haloalkyl, halogen, an electron withdrawing group or Cé-C | 2 ayl that is substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; and both R20 and R2 are either hydrogen or halogen; characterized in that a compound of the formula II is oxidized and the resulting intermediate of the formula I is hydrogenated and / or halogenated.

Iji ^ t 8

The above process can also be carried out in a manner in which the intermediate of the formula I is derivatized to become a different structure of the formula I before being hydrogenated and / or halogenated, e.g. by esterification, dimerization, trimerization or polymerization; or wherein the intermediate of the formula I is first hydrogenated and then further derivatized, e.g. by esterification, dimerization, trimerization or polymerization.

Preferred is a process for the preparation of a compound of the formula V, wherein R is an organic linking group containing 2-500 carbon atoms and which together with the carbon atoms to which it is directly bonded and the nitrogen atom is 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 6 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 C5 -C12 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 2 aryl, C 1 -C 4 haloalkyl, an electron withdrawing group or C 6 -C 2 aryl substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; R7 and R8 H, C1 -C8 alkyl, C3 -C8 alkenyl, C5 -C12 aryl, C1 -C4 haloalkyl, halogen, an electron withdrawing group or C6 -C22 aryl substituted with a radical selected from C, -C4 alkyl, C1 -C4 alkoxy, halogen; and both R20 and R21 are either hydrogen or halogen.

The most preferred products of the method of the present invention are those of formulas IIIc, IVa and Va, which are described below.

In general, all products of the present process can be used as organic matter stabilizers against the deleterious effects of light, oxygen and heat. Of particular interest are the compounds of formulas I, Ia, III, IV, and V. Best results are obtained with compounds of formula III, wherein R, R 1, R 2, R 3, and R 4 are as defined for the formula I and R5, R6, R7, Rg and R9 independently of one another H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 2 aryl, CN, COOR 10, where R 10 is as defined for formula I, or C6-C1210i; o c: $ 9 aryl substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy. Organic material that is most effectively stabilized by the subject compounds is organic polymer material described below, such as e.g. coatings and thermoplastic bulk polymers, films or fibers. When the polymers come into contact with a pesticide, e.g. a pesticide containing sulfur and / or halogen atoms, the products of the present process achieve stabilization against both light and the deleterious effects of the pesticide. This is especially important for polymers, e.g. films, tapes or fibers which are used in agriculture, mainly polyolefins such as PE or PP or polyolefin-10 copolymers. Preferred compounds in this field are those of formula III, especially those of formula IIIc below.

An important application of all products according to the present method is the stabilization of paper and pulp, in particular paper and pulp still containing lignin, against yellowing. The use of the present products 15 can be effected as described, for example, in International patent application WO 98/04381 and the corresponding US patent application 09/119567 and the publications cited therein. Most preferred for this application is the use of a monomeric compound of the formula III, e.g. a compound where R is C3 -C12 alkylene or C4 -C12 alkylene interrupted by O, NH, OCO or NHCO, R, -R4 are methyl or ethyl, especially methyl and Rj-R, each H or C 1 -C 4 alkyl, especially H; examples are 1-propyloxy-2,2,6,6-tetramethyl-piperidine, 1-propyloxy-2,2,6,6-tetramethylpiperidin-4-one or the product of present Example IVa (see below).

Furthermore, the products of the present process can advantageously be used as flame retardants for organic polymers. Thus, by using the products of the present invention, an organic polymer is stabilized against the deleterious effects of light, oxygen and heat while effectively reducing the flammability of the polymer. The use of the present products can take place as described, for example, in International patent application WO 98/13469 and the corresponding US patent application 09/104718 and the publications cited therein, as well as EP-A-792911 or US-A-5393812. Most preferred for this application is the use of a compound of the formula III or V, in particular 101 IS / 4 »10 that of the formula IIIc below or of the formula V, wherein at least one of the radicals Rs, R6 R7, R8, R18, R20 or R21 is halogen, especially bromine. The subject compounds can be used individually as flame retardants or can be used in combination with known flame retardants, such as a flame retardant selected from the halogenated phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrates and metal oxides or mixtures thereof.

Furthermore, it was a finding of this invention that some compounds of the formula III are particularly well suited as stabilizers for organic matter against the deleterious effects of light, oxygen and heat.

The invention therefore also provides compositions comprising A) an organic polymer sensitive to oxidative, thermal and / or actinic degradation and B) at least one compound of the formula IIIa, IVa or Va 15 RV2 R'i; NOCC — CH, (lilac) V h2 H2 20 R3 / r4 V2 r> N — O — r— ~~ ^ - R 6 «Va) 25 X l, B» R3 / R “10 1 130 4 t 11 R R2

X Re R, RS

R N-0 ---- R 6 (Va) / N R 9 R 20 R 21 R, 7 r4 where 10 h 2 c-R 'and R each are an organic linking group of the formula e ((VI);

There is E2 —CO— or - (CH2) p— where p is 0, 1 or 2; 15 is E, a carbon atom containing two radicals R24 and R25, or> N-R25, or oxygen, and R24 and R25 being hydrogen or an organic radical, characterized in that the linking group R contains 2-500 carbon atoms in total and together with the carbon atoms to which it is directly bonded 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 6 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 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C5 -C12 cycloalkyl; R5, R6, R7, Rg and R, independently of one another H, C, -Cg alkyl, C2-Cg alkenyl, C5-Cl2 aryl, C, -C4 haloalkyl, an electron withdrawing group or C6-C22 aryl which is substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; R20 and R2I are halogen; and R22 and R23 are hydrogen or together are a chemical bond.

30 h2 r c—

Usually R 'in formula IIIa is not the linking group, where R 25 are C-1011334 12 R24 and R25 together = 0 or where R24 is hydrogen and R2S is hydrogen or hydroxy.

Preferred is the formula lila wherein R 'is a C7-C500 hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen and which 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.

The present invention further provides the use of compounds of the formula lila for stabilizing organic polymers against oxidative, thermal or actinic degradation. The invention further comprises a method for stabilizing organic polymers against thermal, oxidative and / or actinic degradation, comprising adding at least one compound of the formula IIIa to the polymer.

More detailed examples of sterically hindered amines are described below in classes (a ") to (j").

15 (a ’) A compound of the formula (la)

CH3 G

G - / 'G - \ O - G12 20 G - CHf \' (1a) CH3 "1 where n, is a number from 1 to 4, G and G are independently hydrogen or methyl, G ,, n-propoxy, O-CH = C = CH2, O-CH = CH-CH3 or halogenated n-propoxy, especially n-propoxy, or brominated n-propoxy; G) 2, when η, 1 is hydrogen C 1 -C 18 alkyl which is not interrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent moiety 30 of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid with 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid with 7 to 15 carbon atoms, or an α, β-unsaturated carboxylic acid 101, 8, 4, 13 with 3 to 5 carbon atoms or an aromatic carboxylic acid having 7 to 15 carbon atoms, each carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety having 1 to 3 CO O12 groups can be substituted, where Z12 is H, C1 -C20 alkyl, C3-C12 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl, 5 G | 2, when n is 2, C2-C, 2 alkylene, C4-C12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably an aliphatic dicarboxylic acid radical of 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid of 8-14 carbon atoms or of an aliphatic, 10 cycloaliphatic or aromatic dicarbamic acid of 8-14 carbon atoms, any dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety having one or two —COOZ, 2 groups substituted, G | 2, when n, 3 is a trivalent residue of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic residue with -COOZl2, or of aromatic tricarbamic acid o f is of a phosphorus-containing acid, or is a trivalent silyl radical, and Gi2, when n, is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The above-mentioned carboxylic acid residues in any case mean residues of the formula (—CO) xR, wherein x is as defined above and the meaning of R derives from the given definition.

For example, alkyl of up to 20 carbon atoms is methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl , n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Examples of various G) 2 residues are given below.

If G | 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or p- (3,5-di-tert-butyl-4-hydroxyphenyl propionyl residue.

For example, if G | 2 is a monovalent silyl residue, it is a residue with the formula - (CjH2j) —Si (Z ') 2Z ", where j is an integer from 2 to 5 and Z' and Z", independently of one another, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.

When G | 2 is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, III. ... .... · 14 »phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl (3,5-di-tert-butyl-4-hydroxy-benzyl) malonyl or bicycloheptenedicarbonyl radical or a group of the formula

O

you-

H, C ° - <^ J) -CH = C

10 r ~ o

When G, 2 is a trivalent residue of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl residue.

When G12 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

When G, 2 is a divalent radical of a dicarbamic acid, it is, for example, a hexamethylenedicarbamoyl or 2,4-tolylene dicarbamoyl radical.

Preference is given to compounds of the formula (1a), wherein G

and G, are hydrogen, Gn is hydrogen or methyl, n is 2 and G, 2 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.

(b ’) A compound of the formula (lb) 25 Γ Ί

CH3 G

g-ch2 ^ J_ / ’G13 G ~ \ / ~ N G» (1b) G - ch3 n2 where G and G are independently hydrogen or methyl, G, | n-propoxy is 1011394 30 15

Gi 3 hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C, -C, g alkanoyl, C3-C 5 alkenoyl, benzoyl or a group of the formula (lb-1) 5 H3 G, g ~ ny - (1 b-1) G-CHf \ 'ch3 10 n2 is the number 1, 2 or 3; and G | 4, when n2 is 1, hydrogen, C1 -C8 alkyl, C3 -C8 alkenyl, C5 -C7 cycloalkyl, C1 -C4 alkyl substituted with a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula —CH 2 —CH (OH) —Z or of the formula 15 —CONH-Z, wherein Z is hydrogen, methyl, or phenyl;

G14, when n2 is 2, C2 -C12 alkylene, C6 -C2 arylene, xylylene, a —CH2 — CH (OH) —CH2 group or —CH2 — CH (OH) —CH2 —O-D-O - group is where D is C2-C10 alkylene, C6-C | arylene, C6-C12 cycloalkylene or, provided G3 is not alkanoyl, alkenoyl or benzoyl, where G4 is also 1-oxo -C 2 -C 12 alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or further the group -CO-,

G14, when n, is 3, a group O 25 -CH2CH (OH) CH2 ^ JL / CH2CH (OH) CH2-

N N

O ^ N- ^ O

CH2CH (OH) is CH2-30 or, when n2 is 1, Gl3 and Gl4 together may be the divalent moiety of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

10: '; 16

Some examples of residues Gl3, Gl4 and D are given below.

The alkyl substituents are as defined in (a) above.

C5-C7 cycloalkyl substituents are especially cyclohexyl.

Gn as C7-Cg aralkyl is in particular phenylethyl or preferably benzyl.

5 G, 3 as C 2 -C 5 hydroxyalkyl is in particular 2-hydroxyethyl or 2-hydroxypropyl.

Gn 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 especially acryloyl.

10 G | 4 as C 2 -C 6 alkenyl is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

Gu as C 1 -C 4 alkyl substituted by hydroxy, cyano, alkoxycarbonyl or carbamide may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxy-carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylamino-15-carbonyl-methyl) .

C2-C12 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethyl-propylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecomethylene.

C6-C15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene 20 or 4,4'-diphenylene.

C6-C12 cycloalkylene is in particular cyclohexylene.

G 4 as 1-oxo-C 2 -C 12 alkylene is preferably a group O CH 3 CH,

Preference is given to compounds of the formula (lb), wherein n2 is 1 or 2, G and G are hydrogen, G3 is hydrogen, CrCl2 alkyl or a group of the formula

rj Λ * O: Π A

j U i i v · 'v · »· ^ * 17 G-CH2 ~ ^ V's TV“

G - CH ^ I

CH3 and Gi4 in case n2 = 1 is hydrogen or C1 -C12 alkyl and in case n2 = 2 is C2 -C8 alkylene or 1-oxo-C2 -C8 alkylene.

(c ’) A compound of the formula (lc) CH3 \ 3 Gi g-ch2 ^) / 15 GiT-N ^ Gis (1C)

O

G - CH.fl ch3 n3 where n3 is the number 1 or 2, G, G, and G ,, are as defined in (b ') and G1, when n3 is 1, C 2 -C 6 alkylene, C 2 -C 6 hydroxyalkylene or C4-C22 is acyloxyalkylene and when n3 is 2, G | 5 is the group (—CH2) 2C (CH2—) 2.

G5 as C 2 -C 6 alkylene or C 2 -C 8 hydroxyalkylene is, for example, ethylene, 1-methyl ethylene, propylene, 2-ethyl propylene or 2-ethyl-2-hydroxymethyl propylene.

For example, G, 5 as C4-C22 acyloxyalkylene is 2-ethyl-2-acetoxymethyl-propylene.

101 13J4 t 18 (d ’) A compound of the formula (ld-1), (ld-2) or (ld-3)

5 CH3 916 O

- «. > * "G - CV \ f \ || CH3 o L J n4 10 9H3 g, f g-ch20 / o — c — t2 G-N ^ X | <1d-2) 7 N-Cs

15 G-CHr1T A

g-ch2 ^ 1% Gi o-c-t2 20 GlTV) <| g-ch ^ v-7 rN 6.7 (1d'3) ch3 o L n4 25 where n4 is the number 1 or 2, G, G, and Gn are as defined at (b '), G (6 hydrogen C 1 -C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl and Gn, when n 4 is 1, hydrogen, C 1 -C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C) O aryl, glycidyl or a group of the formula - (CH2) p-COO-Q or - (CH2) p-O-CO-Q, where p 1 or 2 and Q is C 1 -C 4 alkyl or phenyl, and

Gn, when n is 2, C2-C12 alkylene, C4-C12 alkenylene, C6-C12 arylene, a group of the formula -CH2-CH (0H) -CH2-O-D'-O-CH2-CH (0H) -CH2-, wherein D 'C2-C10 1011334-19 is alkylene, C6-C15 arylene or C6-C12 cycloalkylene, or a group of the formula —CH2CH (OD ") CH2— (OCH2-CH (OD") CH 2) - wherein D "is hydrogen, C 1 -C 18 alkyl, allyl, benzyl, C 2 -C 12 alkanoyl or benzoyl, T, and T2, independently, is hydrogen, C 1 -C 18 alkyl or unsubstituted or with 5 halogen or C1 -C4 alkyl substituted C6 -C10 aryl or C7 -C9 aralkyl or T, and T2 together with the carbon atom to which they are attached form a C5 -C14 cycloalkane ring.

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

Some examples of the various variables in formulas (1d-1), (ΜΙ 0 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 can be, for example, the above-mentioned groups 15 and further, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C2-C6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxy-methyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

G17 as C3-C5 alkenyl is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

G | 7, T, and T2 as C7-C9 aralkyl are in particular phenethyl or preferably benzyl. When T 1 and T 2 together with the carbon atom form a cycloalkane ring, it may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

G17 as C 2 -C 4 hydroxyalkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

G | 7, T | and T2 as C6 -C10 aryl are in particular phenyl or α- or β-naphthyl, which are unsubstituted or substituted with halogen or C 1 -C 4 alkyl.

Gn as C 2 -C 12 alkylene is, for example, ethylene, propylene, 2,2-dimethyl-30 propylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecemethylene.

G17 as C4-Cl2 alkenylene is in particular 2-butenylene, 2-pentenylene or 3-hexenylene.

101 13 9 4 »20 O ,, as C6-C | 2 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, dodecanyl, but preferably acetyl.

For example, 5 D "as C2-C10 alkylene, C6-C15 arylene or C6-C, 2 cycloalkylene has one of the definitions given for D at (b").

(e ’) A compound of the formula (le) Γ?“ 1

i ° I

n 'n --G »<, e>

nS

15 where n5 is the number 1 or 2 and G, g is a group of the formula ch3 G, ch3g, G - / G — CH2 ^ __ ^ G2 G - M Grrl \ _ / N __ (A) * rE ~~

20 g-ch2 ^ I g ~ ch ^ L.

CH3 CH3 where G and Gn are as defined in (b ') and G, and G2 are hydrogen, methyl or together a substituent = 0, 25 is EO-or-ND "-, A is C2-C6 alkylene or - ( CH2) is 3 —O— and x, the number is 0 or 1, D is "hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalky], G | 9 is identical to Glg or one of the groups —N (G21) (G22), —OG23, -N (H) (CH2OG23) or —N (CH2OG23) are 2, G20, if n = 1, identical to G) g or G19 and if n = 2 is a group —E — DIV — E—, where DIV is C2-C8 alkylene or C2-C8 alkylene interrupted by 1 or 2 groups —NG2is, 101 13 3 4 21 G21 C 1, C 1 2 alkyl, cyclohexyl , benzyl or CrC4 hydroxyalkyl or a group of the formula

, ^ <3. 1 TCH

5 G-CH. / -V 3 a ~ \ _) - or G-vJ> - 11-11ΐ — ν_Λ ° "'G - CH2 ^ |' H3C '| n-C4H9 n-C4H9 PCH3 ch3 ch3 ch3 10 is G22 C | -C 2 alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl and G 23 is hydrogen, C 1 -C 2 alkyl or phenyl, or G 2 and G 22 together are C 4 -C 5 alkylene or C 4 -C 5 oxa-alkylene, for example —CH 2 CH 2 -O-CH2CH2 - or a group of the formula -CH2CH-N (G ,,) - CH2CH2-.

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

C 1 -C 2 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.

C5-C7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

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

When G21 and G22 together are C4-C5 alkylene or oxa-alkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this class are those having the following formulas: 101 13 3 4 0 22 o-ch2ch2ch3 5 H3 °> r ^ CH3 H, c ^ r JrCH3 N - n-C4H9 CH3 I ch3

H3C ^ Y — L N 'N

IQ H3CCH2CH2-Ö - N y-N-U N -N - \ __ / N ~ 0-CH2CH2CH3

H 3 C 4 Y n -C 4 H 9 n "C 4 H 9" OH

CH 'ch3 15 (f) A compound of the formula (If) H3 ^ CH3 *> - N ^ N— (N — G “(11) 20”> VHj y- \ III h3c ch3 G „-N) - N M- ^

V

h3c ch3 25 where G is as defined in (b).

(g ') Oligomeric compounds or polymers, the repeating structural unit of which contains a 2,2,6,6-tetraalkylpiperidinyl radical, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and copolymers thereof containing such residues.

Examples of 2,2,6,6-polyalkylpiperidine compounds of this class are those of the following formulas, wherein m, through m, 4 is a number 1011394 23 from 2 to about 200, preferably 2 to 100, for example 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 of the oligomeric compounds or polymers listed below depend on the methods used to prepare the compounds. The end groups can also be further modified after the synthesis of the compounds. Examples are compounds of the formula (1 g-1) io -N-R '^ ~ N-- V R Λ B 11 H3CJ) / CH3 Η30 ^ νΎη3 0 CHp 15 | 2 CH? I 2 CH 3 J n 20 wherein the index n ranges from 1 to 15, especially from 3-9;

R 12 C2-C | 2 alkylene, C4-C12 alkenylene, C5-C7 cycloalkylene, Cs-C7 cycloalkylene di (C, -C4 alkylene), C, -C4 alkylene di (C5-C7 cycloalkylene), phenylene di (C, -C4 alkylene) or C4-C12alkylene interrupted by 1,4-piperazine diyl, —O— or> N-X “where X, CrC (is 2 acyl or (C 1 -C 12 alkoxy) carbonyl or one of the definitions of R, 4 25 below has except hydrogen; or R12 is a group of formula (Ib ') or (Ic'); -CH-CH-CH, - "b '> 0 30 0 = 0 • i P' O 1 24 O / -O 5 where m is 2 or 3, X 2 is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; phenyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; C7-C9 phenylalkyl which is unsubstituted or which is substituted on the phenyl group by 1, 2 or 3 C -C4 alkyl groups; and radicals X3 independently of each other are C2-C12 alkylene; radicals B independently of one another Cl, —10Rn, —N (R14) (R15) or a group m et are the formula (IIld); 15 H.C CH,

r ~ K

-X— (N O — C C CH 3 (illd) \ - / H2 H2 h3c ch3 20

Ru, R14 and R15, which are the same or different, hydrogen, C1 -C18 alkyl, C5 -C12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C1 -C4 alkyl groups; C3 -C18 g alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; C7-C9 phenylalkyl which is unsubstituted or which is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl or C 2 -C 4 alkyl which is substituted 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 "); Ί \ i— 30 N-1 where Y is —O—, —CH2—, —CH2CH2— or> N-CH3, or —N (Rm) (R | 5) is further a group of formula (Ie ') ; 101132- 25 is X — O— or> N — R16;

R 16 is hydrogen, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C7-C9 phenylalkyl which is unsubstituted or is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl-5 groups; tetrahydrofurfuryl, a group of the formula (Illf) H, CH,

r ~ K

- (N-OCC-CH. (Illf) H 2 H 2 h 3 c ch 3 10 or C 2 -C 4 alkyl which is substituted 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 '); R 1 has one of the definitions given for R 6.

In these compounds, the end group bonded to the triazine residue can be, for example, a group B or -N (R ,,) -R, 2-B, such as chlorine or a group

-N- (CH2) 6 -N-H

H3C CH3 H3C ~ ^ jCj ^ CH3 H3C CH3 h CI CHa G „G« and the end group bonded to the diamino group can be, for example, hydrogen or a di-B-substituted triazinyl group, such as a group —ci * ci γ ch3 ch3 ΝγΝ 30 HN-C - CH — C — CH3 HN-Y ƒ CH3 CH3 i Ü sij ύ: t 26

It may be convenient to replace the chlorine bound to triazine with e.g. —OH or an amino group. Suitable amino groups are usually: pyrrolidin-1-yl, morpholino, —NH 2, —N (C 1 -C 8 alkyl) 2 and —NY “(C 1 -C 8 alkyl), wherein Y 1 is hydrogen or a group of the formula H 3 C CH3 PP 'h3c ch3 is 10.

In the oligomeric compounds and polymers shown above, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-15-butyl, 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, tri-decyl, tetradecyl, pentadecyl, hexadecyl , heptadecyl, octadecyl, eicosyl and docosyl; 20 are examples of cycloalkyl cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; is an example of C7-C9 phenylalkyl benzyl; and are examples of alkylene ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.

(H ') A compound of the formula (1h) CH3 n "G - G —N N - G14 \ -jm G-CHfl 30 L CH3 J n n6 where n6 is the number 1 or 2, G and G, , are as defined in (a ') and G 4 is 101 109 4 27 as defined in (b').

(i ') A compound of the formula (li) 5 G39 \ y ^ N \ / G39 T ll (1 i) ΝγΝ G39 10 wherein the residues G39, independently of each other, are a group of the formula (li-1) H, C ρμι 0y ^ CHs -N-G4 - NN G42 (1i-1) GT \ 15 40 H3C CH3 where G40 is C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl, G 4 is C 2 -C 12 alkylene and G42 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 with C 1 -C 4 alkyl; or C 1 -C 6 is acyl.

Alkyl is, for example, C 1 -C 4 alkyl, especially 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.

Particular preference is given to a compound of the formula Illb ^ r <- - Ί i U! ; o -v t 28

A --- N-R 12 “-N - ^ - A

s nvn l A nyn B 11 H3 CJ [J / CH3 i h3c n ^ ch3 (lilb) 0 ch2 10 CH3 Π 15 with radicals A independently —OR13, —N (RI4) (RI5) or a group containing the formula (Hid); h3c ch3 20 / -x-ί N-O-C-C CH3 (Hid) \ Y ** 2 h3c ch3 25 X -O or> N-R16; R 6 hydrogen, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 5 -C 2 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C7-C9 phenylalkyl which is unsubstituted or is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl, a group of the formula (Illf) 30 Hi CH3 - ('N-OC-C-CH3 (Illf) Y_ ^ h2 h2 h3c ch3 1 O 1' 5 0 0/1 I Vj i, v ,;, J 1: i '»29 or C 2 -C 4 alkyl which is substituted 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 ');

Ru has one of the definitions given for R16; and residues B independently have one of the definitions of A; and 5 wherein the formula (Ie ") and all other symbols are as defined above in formula Ia.

The residues B, R 1 and R 12 in the individual repeating units can be the same or different within the given meanings.

(j ’) A compound of the formula (2a) 10 R2 o CH - CH, -CH.-0 - NO (2a)

R-'V

3 R4 15 where

R 1, R 2, R 3 and R 4 independently of one another are C 1 -C 6 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 2 cycloalkyl 20, or R 3 and R 4 together with the carbon to which they are attached are C5 -C12 cycloalkyl.

Specific examples of hydrogenated products of the present invention include the following compounds: 1-propoxy-2,2,6,6-tetramethyl-4-piperidone, 25 1-propoxy-2,2,6,6-tetramethyl-4-piperidol , bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) - (3 \ 5'-di-tert-butyl-4'-hydroxy-benzyl) butyl malonate, bis (1-propoxy-2 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) succinate, 30 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-piperidineamine, 5- (1-propoxy- 2,2,6,6-tetramethyl-4-piperidyl) -2-cycloundecyloxazole, 1,6-hexanediyl-N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidylformamide) , 1 o -i ·:;:; 1.5-dioxaspiro (5.5) indecan-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) -Γ, 3 ', 5'-triazine-6'-yl) -1,5,8,12-tetra-azadodecane, 5 1,3,5-tris (N-cyc) ohexyl-N- (1-propoxy-2,2,6,6-tetramethylpiperazine-3-on-4 -yl) amino) -s-triazine, linear or cyclic condensation products of N, N'-bis (1-propoxy-2,2,6,6-tetra-methyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino- 2,6-dichloro-1,3,5-triazine, 10 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-butane-tetracarboxylate, 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, 15 3-n-octyl-8-propoxy-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, linear or cyclic condensation products of N, N'-bis ( 1-propoxy-2,2,6,6-tetra-methyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro-4,6 -bis (4-n-butylamino-1-propoxy-2,2,6,6-tetra-methylpiperidyl) -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) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-1-propoxy-2,2,6,6-tetramethyl-piperidine, a condensation product of N, N 1'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -25 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 as well as 4-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidine; N- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-8-propoxy-7,7,9,9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro [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, a Π Ί i C ', 1 31 poly (methylpropyl-3-oxy-4- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride α-olefin copolymer with 1-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine; or the compound 5 CH2CH2CH3 R-NH- (CH2) 3-N (R) - (CH2) 2-N (R) - (CH2) 3-NH-R, with O q'CH2CH2CH3 - Xf-Xf-10 c4h9 / n> VN "c4h9

NyN

The compounds of formulas I, III and V, in particular Ilia and Illb, can advantageously be used for stabilizing organic material against the deleterious effect of light, oxygen and / or heat, in particular for stabilizing synthetic organic polymers or compositions containing them. They are characterized by high thermal stability, compatibility with the substrate and good persistence in the substrate.

Examples of polymers that can be stabilized in this way are the following: 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloalkenes, such as, for example, cyclopentene or norborin; further polyethylene (which may optionally be cross-linked), for example high density polyethylene (HDPE), high density polyethylene, high molecular weight (HDPE-HMW), high density polyethylene and ultra high molecular weight (HDPE-UHMW), polyethylene with medium density (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins shown in the previous paragraph, especially polyethylene and polypropylene, can be prepared by various, and in particular the following, processes: a) radical polymerization (usually under high pressure and at elevated temperature (1011394 32).

b) by means of a catalyst, the catalyst usually containing one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups, which can have either a π or a σ coordination. These metal complexes can be in the free form or they can be fixed on supports, such as, for example, on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts may be active as such in the polymerization or further activating agents may be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, these metal elements being groups Ia, Ha and / or lilac of the Periodic System.

The activating agents can, for example, be modified with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metallocene, or Single-Site (SSC) catalysts.

2. Mixtures of the polymers mentioned under 1), for example, mixing of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different kinds of polyethylene (for example LDPE / HDPE).

3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butylene 1 copolymers, propylene / isobutylene copolymers, ethylene / butene-1 copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymer, 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 (ion polymers), as well as of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norborne; further mixtures of such • • r>; "- / ius; ·· - .. * * 33 copolymers with each other and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA ), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or statistically constructed polyolefin / carbon monoxide copolymers and mixtures thereof with other polymers, such as, for example, polyamides.

Hydrocarbon resins (e.g. C5-C9), including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyolefins and starch.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate and methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact blends of styrene copolymers and another polymer, such as, for example, a polyacrylate, a diene-15 polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as, 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 resp. alkyl methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), which are known for example as ABS, MBS, ASA or AES polymers .

8. Halogen-containing polymers, such as, for example, polychloroprene, chlorinated rubbers, the chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, particularly polymers of halogen-containing vinyl compounds, such as, for example, vinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; butyl acrylate-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers, acrylonitrile / vinyl halide copolymers or acrylonitrile copolymers / alkyl meth acrylate / butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as the copolymers thereof with the olefins mentioned under 1).

12. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes, which contain comonomers, such as, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from polyethers, polyesters and polybutadienes having hydroxyl end groups on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from amino carboxylic 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-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further polyamides or copolyamides modified with EPDM or ABS; as well as condensed polyamides during processing ("RIM polyamide systems").

17. Polyurea, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylolcyclohexane terephthalate, polyhydroxy benzoates, as well as block copolyether esters derived from polyethers with hydro- xyl end groups; further polyesters modified with polycarbonates or MBS.

19. Polycarbonates and Polyester Carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cross-linked polymers derived from aldehydes on the one hand and phenols, urea or melamines on the other, such as phenol / formaldehyde, urea / formaldehyde 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, as well as vinyl compounds as cross-linking agents, and their halogen-containing modifications with low flammability.

24. Cross-linkable acrylic resins derived from substituted acrylic acid esters, such as, for example, from epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, products of diglycidyl ethers of bisphenol-A and bisphenol-F, which are cross-linked with conventional curing agents, such as, for example, anhydrides or amines, with or without accelerators.

101 1334 * 36 27. Blends (polyblends) of the aforementioned polymers, such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTB / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylics, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS, PPO / HIPS, 5 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 compounds of formula IIIa as stabilizers in synthetic organic polymers, for example, a coating or a bulk polymer or article made therefrom, particularly in thermoplastic polymers and similar compositions as well as in coating compositions. Thermoplastic polymers that are most important in the present compositions are polyolefins and their copolymers, as mentioned at 1-3 above, thermoplastic polyolefin (TPO), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), polycarbonate, as above at 19, and blends, as above at 28. Of paramount importance are polyethylene (PE), polypropylene (PP), polycarbonate (PC) and polycarbonate blends such as PC / ABS blends, as well as in acid or metal catalyzed coating compositions.

In general, the compounds of the present invention are added in amounts of 0.1 to 10%, preferably 0.01 to 5%, especially 0.01 to 2% (based on the material to be stabilized). stabilize material added. The use of the new compounds in amounts of 0.05 to 1.5%, in particular 0.1 to 0.5%, is particularly preferred. When compounds of the present invention are used as flame retardants, the doses are usually higher, such as e.g. 0.1 to 25% by weight, mainly 0.1 to 25% by weight of the organic material to be stabilized and protected against inflammation.

The incorporation into the materials can be carried out, for example, by mixing or applying the compounds of the formula I, Ilia, IV, V and, if desired, further additives according to methods customary in the art. In polymers, especially synthetic polymers, the incorporation can take place before or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. Elastomers can also be stabilized as latices. A further possibility for including the compounds ^ β 1 I ^ ύ? 37 of the formula lilac in polymers is the addition thereof before, during or immediately after the polymerization of the respective monomers or before cross-linking. In this context, the compound of the formula lilac may be added as such or else in encapsulated form (e.g., in waxes, oils or polymers). In the case of the addition before or during the polymerization, the compounds of the formula lila can also act as a chain length regulator of the polymers (chain terminator).

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

The compounds of the formula lila can be incorporated judiciously by the following methods: as an emulsion or dispersion (eg with latices or emulsion polymers), as a dry mixture during the mixing in of additional components or polymer mixtures, by direct addition to the processing equipment ( (eg extruders, internal mixers, etc.), as a solution or melt.

New polymer compositions can be added in various forms and / or processed into various products, such as, for example, films, fibers, belts, molding compositions, profiles or as binders for coatings, adhesives or kits.

In addition to the compounds of the formula IIIa, the new compositions may comprise as additional component C one or more conventional additives, such as, for example, those shown 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-butyl-phenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methyl-30-cyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as eg 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1 '-ylphenol, 2,4-dimethyl-6- (1' -methylheptadec-1 '-yl) phenol, 2,4-dimethyl-6- (1 '-methyl- 101 13 3 4 * 38 tridec-l'-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.

5 1.3 Hydroquinones and alkaline 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-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

10 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 Alkvlidene bisphenols. for example 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl-6- (α-methylcyclohexyI) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4.6 di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2 1'-methylene bis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylene bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene bis (2,6- di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyljbutane, 2.6 -bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-25 tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1 bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl] butyrate], bis (3 -tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl ) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy-phenyl-propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 O-, N- and S-benzyl compounds. for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, 101 139 4 t 39 tridecyl-4-hydroxy-3,5 -di-tert-butylbenzyl mercaptoacetate, 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-hydroxy-benzyl mercaptoacetate.

5 1.8 Hydroxylated malonates. for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecyl mercaptoethyl- 2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) malonate, di [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.

10 1.9 Aromatic hydrogen hydroxide 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-hydroxy-benzyl) phenol.

1.10 Triazine compounds. for example 2,4-bis (octyl mercapto) -6- (3,5-di-tert-15-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3.5 -di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxy-phenoxy) -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-hydroxyphenyl-ethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1.3.5-triazine, 1, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11 Benzyl Phosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxy-benzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate dioctadecyl-5-tert-butyl-4-hydroxy-3-methyl-benzylphosphonate, the Ca salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxy-benzylphosphonic acid.

1.12 Acvlaminophenols. e.g. 4-hydroxylanric acid anilide, 4-hydroxystearic acid anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.

1.13 Esters of B- (3,5-di-tert-butyl-4-hydroxylphenyl) proDionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopethyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl ) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaunde- 101 139 4 40 canol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2. 2] octane.

1.14 Esters of B- (5-tert-butyl-4-hydroxyl-3-methylphenyl Dropionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, n-octanol, iso-octanol, 5 octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neo-pentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaun decanol, 3 -thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15 Esters of B-f3.5-dicvclohexyl-4-hydroxylphenylpropionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N bis-(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-15 thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16 Esters of 3,5-di-tert-butyl-4-hydroxylphenylacetic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thio-diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6.7-trioxabicyclo [2.2.2] octane.

1.17 Amides of B-3.5-di-tert-butyl-4-hydroxylphenyl) propionic acid. such as e.g.

N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N 1'-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).

30 1.19 Amine antioxidants. such as e.g. 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, Ν, Ν'-dicyclohexyl-p-phenylenediamine, Ν, Ν'-diphenyl- p-phenylene- 101 13 9 4 * 41 diamine, N, N'-di (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-toluene-sulfamoyl ) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenyl-5 amine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoyl-aminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxy-phenyl) amine, 2,6-di -tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl-10 methane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenyl-methane, 1,2 -di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (r, 3'-dimethylbutyl) phenyl] amine, tert-octylated N phenyl-1-naphthylamine, a mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and di-alkylated nonyldiphenylamines, a mixture of 15 mono and di-alkylated dodecyldiphenylamines, a mixture of mono and di-alkylated isopropyl / isohexyldiphenylamines, a mixture of mono and di-alkylated tert-butyl diphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine mono- and di-alkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine-20ne, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2, 6,6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6, 6-tetramethylpiperidin-4-ol.

2. UV absorbers and light protectors 2.1 2- (2, -Hydroxyphenylbenzotriazoles. Such as 2- (2'-hydroxy-5'-25 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-chloro-benzo-triazole, 2- (3'-tert-butyl-2'-hydroxy-5'- methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxy-30 phenyl) benzotriazole , 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2 - (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2- ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-s., λ ·· /; yj W i! ij t »42 butyl-2 -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl -2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2 - (3 '-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] - 2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-5-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyl) oxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benztriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 "- (2-methoxy-carbonylethyl) -2" -hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2] 2- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzo-triazol-2-ylphenyl, 2- [2'-hydroxy-3 ' - (α, α-dimethylbenzyl) -5 '- (1,1,3,3-tetramethyl-butyl) phenyl] benzotriazole; 2- [2'-Hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (a, a-dimethylbenzyl) phenyl] benzotriazole.

2.2 2-hydroxybenzophenones. such as, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4-trihydroxy, 2'-hydroxy- 4 .4'-dimethoxy derivative.

2.3 Esters of optionally substituted benzoic acids, such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxy-2-hydroxy , 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 Acrvaten. such as, for example, α-cyano-P, β-diphenylacrylic acid ethyl ester, respectively. isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester, respectively. -butyl ester, α-carbomethoxy-p-methoxycinnamic acid methyl ester and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5 Nickel compounds. such as, for example, nickel complexes of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of the monoalkyl esters, eg the methyl 30 or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5- hydroxypyrazole, optionally with additional ligands.

2.6 Sterically hindered amines. such as, for example, bis (2,2,6,6-tetramethyl-4-4 π i ^ 4 1 UI! V "1 43 piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-penta-methyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,6,6,6-pentamethyl-4-piperidyl) ester, the condensation product of 1- (2-hydroxyethyl) -2,2,6 6-tetramethyl-4-5 hydroxypiperidine and succinic acid, linear or cyclic condensation products 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, tetra-kis (2,2,6,6-tetramethyl-4-piperidyl) -1,2 3,4-butane tetracarboxylate, 1,1- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4- 10 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 condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-15 diamine and 4-morpholino -2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5 -triazine and 1,2-bis (3-aminopropylamino) ethane, the condensation product of 2-chloro-4,6-di (4-n-butyl-amino-1,2,6,6,6-pentamethylpiperidyl) -1 , 3,5-triazine and 1,2-bis (3-aminopropyl-amino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane -2,4-20 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-hexa-decyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N, N'- bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-cyclohexyl-amino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis (3-aminopropyl-25 amino) ethane and 2,4,6-trichloro-1, 3,5-triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,6,6,6-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) ethylene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, diester of 4-methoxymethylene malonic acid with 1,2,2,6 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-1: 1: 0;: 44 piperidyl)] siloxane, male reach product neic anhydride α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,6,6,6-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-triazine.

5 2.7 Oxamides. such as, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 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 the mixture thereof with 2-ethoxy -2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy- as well as o- and p-ethoxy-10 di-substituted oxanilides.

2.8 2- (2-Hydroxyphenyl-1,3,5-triazines. Such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) ) -4,6-bis (2,4-dimethyl-phenyl) -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- (2-15 hydroxy-4-octyloxyphenyl 4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-do-decyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyl-oxyphenyl) -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-dimethylphenyl) -1,3,5-triazine, 2- [4-20 (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4, 6-bis (2,4-dimethyl-phenyl) -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-triazi ne, 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) -4-25 (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1 -oxy) -2-hydroxypropyloxyphenyl} -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, the octyl radical being a mixture of different isomers.

3. Metal deactivators. such as, for example, Ν, Ν'-diphenyloxamide, N-salicylal-30 N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionylhydrazine) , 3-salicyloylamino-1,2,4-triazole, bis (benzylidene ioxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, Ν, Ν'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide sali-1 13 9 4 $ 45 cyloyl) thiopropionyl dihydrazide.

4. Phosphites and Phosphonites. such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, di-tert-butyl-phenyl-phenyl-phenyl) phosphite -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 6-tris (tert-butyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert -butyl-12H-dibenz [d, g] -10 1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] - 1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 2,2,2 nitrile [triethyltris (3,3,5,5'-tetra-tert-butyl-1,1-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 , 5,5'-tetra-tert-butyl-l, r-biphenyl-2,2'-diyl) phosphite.

The following phosphites are particularly preferred:

Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy), tris (nonylphenylphosphite, (CH3) 3C% r: ^ sN / C (CH3) 3C.

PP PP

HC — CH P-F J / P 0 CH 2 CH 2 N

jót C (CH3) 3 (CHa) 3C C (CH3) 3 (CH3) 3C L 3 25 (ch3) 3c yyc (ch3> 3 7 V — O-CH2CH (C4H9) CH2CH3 30 ry ° (CH3) 3C- ^ \ A ^ C (CH3) 3 1 O '. 1 IO i> jw' ~ 4 '* 46 5 (OH3) 3C - ^^ - ° -p ^ 3C0'P_O- ^ 3_C (CHs) 3

C (CH3) 3 (CH3) 3C

C (CH3) 3 (CH3) 3C

10 H3C — 0-P P- ° -

C (CH3) 3 (CH3) 3C

Γ ch3 η

15 I

h3c — c — ch3 π ~ u js. / O — P — OCH 2 CH 3 H 37 C, 18 ° C 18 37 H 3 C x X 3, 3 ° VCH 3 J 2 20 5. Hydroxamines such as, for example, Ν, Ν-dibenzylhydroxylamine, Ν, Ν-diethylhydroxylamine, Ν, Ν-dioctylhydroxylamine Ν, Ν-dilaurylhydroxylamine, Ν, Ν-ditetradecylhydroxylamine, Ν, Ν-dihexadecylhydroxylamine, Ν, Ν-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxy-n-decadecyl-n-heptadecyl-hydroxy hydrogenated sebum fatty amine.

6. Nitrons. such as, for example, N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methyl-30 nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl nitron, N-tetradecyl-alpha-tri-decyl nitron, N-hexadecyl -alpha-pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-pentadecyl nitron, N-heptadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-nitronyl-alpha J Ü i i C, yy Ά t 47 Ν, Ν-dialkylhydroxylamine prepared from hydrogenated tallow fatty amine.

7. Thio-energists. such as, for example, thiodipropionic acid dilauryl ester or thiodipropionic acid distearyl ester.

8. Peroxide-destroying compounds, such as esters of β-thio-5-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithio carbamate, dioctadecyl disulfide pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

9 Polyamide stabilizers. such as, for example, copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers. such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg , Na-ricinoleate 15 and K-palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, such as, for example, inorganic substances, such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulphates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids, as well as their salts, such as e.g. 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers, such as e.g. ionic copolymers ("ionomers").

12. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibers, sliver balls, 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, such as, for example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow aids, optical brighteners, flame retardants, antistatic agents and blowing agents.

14. Benzofuranones resp. indolinones. such as, for example, those described in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7- di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl] w ^ «* 48 3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2-one, 3- (4-acetoxy -3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethyl-phenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzo-5 furan-2 -on.

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

Cost stabilizers optionally added to the stabilizer mixture 10 of the invention are preferably further light stabilizers, such as, for example, those of the classes of the 2-hydroxyphenylbenztriazoles, 2-hydroxyphenyl triazines, benzophenones or oxalanilides, e.g. are described in EP-A-453396, EP-A-434608, US-A-5298067, WO 94/18278, GB-A-2297091 and WO 96/28431, and / or other sterically hindered amines derived from 2, 2,6,6-tetraalkylpiperidin-15-dine, containing at least one group of the formula G-CH 2 / CH 3 - x 20 G-CH 2 CH 3, wherein G is hydrogen or methyl, especially hydrogen; examples of tetraalkylpiperidine derivatives that can be used as costabilizers with the mixtures of the invention are given in EP-A-356677, pages 3-17, sections a) to f). These sections of this European patent are considered to be part of the present description.

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

The new coating composition preferably comprises 0.01-10 parts by weight (B), in particular 0.05-10 parts by weight (B), in particular 0.1-5 parts by weight 1011304 »49 (B) per 100 parts by weight of solid binder ( A).

Multilayer systems are also possible here, where the concentration of the new stabilizer (component (B)) in the outer layer can be relatively high, such as, for example, 1 to 15 parts by weight (B), in particular 3-5 parts by weight. (B), per 100 parts by weight of solid binder (A).

The use of the new stabilizer in coatings is accompanied by the additional advantage of preventing delamination, i.e., flaking of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates.

The binder (component (A)) may in principle be any binder customary in industry, such as, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A18, pp. 368-426, VCH, Weinheim 1991 Generally, it is a film-forming binder based on a thermoplastic or thermosetting resin, mainly a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenol, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) can be a cold setting or a hot setting binder; the addition of a curing catalyst can be beneficial. Suitable catalysts that accelerate binder curing are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. Al8, p. 469, VCH Verlags-Gesellschaft, Weinheim 1991.

Preference is given to coating compositions in which component (A) is a binder comprising a functional acrylic resin and a cross-linking agent.

Examples of coating compositions containing specific binders are: 1. paint based on cold or hot crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with addition of a curing catalyst; 2. two-component polyurethane paint based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 1 i 50 ύ 4 50 3. One-component polyurethane paint based on blocked isocyanates, isocyanurates or polyisocyanates, the blocking of which is removed during baking, optionally with the addition of a melamine resin; 4. one-component polyurethane paint based on a trisalkoxycarbonyl-5-triazine cross-linking agent and a hydroxyl-containing resin such as acrylate, polyester or polyether resins; 5. one-component polyurethane paint based on aliphatic or aromatic urethane acrylates or polyurethane acrylates with free amino groups in the urethane structure and melamine resins or polyether resins, if necessary with a curing catalyst; 6. two-component paint based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 7. two-component paint based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester; 8. two-component paint based on carboxyl groups or amino groups containing polyacrylates and polyepoxides; 9. Two-component paint based on acrylate resins containing anhydride groups and a polyhydroxy or polyamino component; 10. Two-component paint based on acrylate-containing anhydrides and polyepoxides; 11. two-component paint 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 paint based on unsaturated polyacrylates and polymalonates; 13. Thermoplastic polyacrylate paint based on thermoplastic acrylate resins or externally cross-linking acrylic 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 light stabilizer of the type of the sterically hindered amines, of the 2- (2-hydroxyphenyl) -1,3, 5-triazines and / or 101 1394 51 2-hydroxyphenyl-2H-benzotriazoles, such as those listed in the above list, for example, in sections 2.1, 2.6 and 2.8. Other examples of photo-stabilizers of the 2- (2-hydroxyphenyl) -1,3,5-triazines type which may be advantageously added may e.g. are found in publications US-A-4619956, EP-A-434608, US-A-5198498, US-A-5322868, US-A-5369140, US-A-5298067, WO 94/18278, EP-A -704437, GB-A-2297091, WO 96/28431. Of particular technical interest is the addition of the 2- (2-hydroxyphenyl) -1,3,5-triazines and / or the 2-hydroxyphenyl-2H-benzotriazoles, in particular the 2- (2-hydroxyphenyl) -1, 3,5-triazines.

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

In addition to components (A), (B) and, if used, (C), the coating composition may also include other components, such as, for example, solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, catalysts for the drying and / or leveling agents. Examples of possible components are those described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A18, pp. 429-471, VCH, Weinheim 1991.

Possible catalysts for drying 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 od Zr, or organometallic compounds such as, for example, 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 the aluminum, titanium or zircon chelates of acetylacetone, ethyl acetyl acetate, salicyl aldehyde, salicyl aldoxime, o-hydroxyacethenone or ethyl trifluoroacetylacetate 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-methyl diethanolamine, N-dimethylethanolamine, N-ethyl sulfine, N-methyl morpholine or diazabicyclo-octane (triethylenediamine) and their salts . Other examples are quaternary ammonium salts, such as, for example, trimethylbenzylammonium chloride.

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

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

The new coating compositions may also be radiation-curable coating compositions. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which are cured after application by actinic radiation, i.e. are converted into a cross-linked, high molecular weight form. If the system cures under the influence of UV, it usually also contains a photoinitiator. Relevant systems are described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol. A18, pp. 451-453. In radiation-curable coating compositions, the new stabilizers can be used without the addition of sterically hindered amines.

The coating compositions according to the invention can be applied to all desired substrates, such as, for example, on metal, wood, plastic or ceramic materials. They are preferably used as a top coat in car finishes. If the top coat comprises two layers, the bottom layer of which is pigmented and the top layer is not pigmented, the new coating composition can be used for either the top or bottom layer or both layers, but preferably the top layer .

The new coating compositions can be applied to the substrates by conventional methods, such as, for example, by coating, spraying, casting, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, volume A18, pp. 491-500.

Depending on the binder system, the coatings can 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, even at higher temperatures.

The coatings obtained according to the invention have excellent resistance to the harmful effects of light, oxygen and heat; in particular, good light stability and resistance to weathering of the coatings thus obtained, for example paint, should be mentioned.

The invention therefore also relates to a coating, in particular a paint, which is stabilized against the harmful effects of light, oxygen and heat with a content of the compound of the formula F according to the invention.

The paint is preferably a top coat for cars. The invention further relates to a method for stabilizing a coating based on organic polymers against damage by light, oxygen and / or heat, comprising mixing a mixture comprising a compound of the formula F with the coating, and to the use of mixtures comprising a compound of the formula F in coating compositions as stabilizers against damage from light, oxygen and / or heat.

The coating compositions may comprise an organic solvent or a mixture of solvents in which the binder is soluble. The coating composition can further be an aqueous solution or dispersion. The medium can also be a mixture of an organic solvent and water. The coating composition may be a high solids paint or may be solvent free (e.g., a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A18, pp. 438-444. For example, the additive of the present invention can be used therein as described, for example, in EP-A-856563, in particular page 22, line 21 to page 26, line 29, and the literature cited in this reference. The powder coating material can also be in the form of a powder suspension (dispersion of the powder in preferably water).

Examples of powder coating resins include: 1. Carboxy and hydroxy functionalized monomer based polyester resins 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® epoxy resins for thermal curing or UV curing with cationic photoinitiators.

3. Acrylate polymers functionalized with hydroxy, carboxy or glycidyl and 1, 4, 4, 54 copolymers. Suitable comonomers include styrene, alkyl methacrylates, acrylamide, acrylonitrile, etc.

4. Unsaturated polyester resins for UV-curable powder coatings, which are usually used together with multifunctional vinyl ethers or acrylate esters.

Resin powder coating with carboxy functionality is usually used in conjunction with cross-linking agents of the following classes: 1) polyfunctional epoxy compounds, such as epoxy resins, triglycidyl isocyanurate, epoxidized unsaturated fatty acid esters (such as Uranox® resins from DSM), and esters of glycidol (such as Araldit® PT910 from Ciba Specialty Chemicals).

2) β-hydroxyalkylamides, such as Primid® types XL552 and QM1260 from Ems Chemie.

3) derivatives of melamine, benzoguanimine and glycoluril, such as Powderlink® 1174 from American Cyanamid.

Crosslinking agents for hydroxy-functional resins include anhydrides and in particular blocked diisocyanates and uretdions etc.

Epoxy-functional resin powder coatings are usually used together with cross-linking agents such as diacids (such as 1,12-dodecanedioic acid), carboxy-functional polyesters, carboxy-functional copolymers of acrylates and methacrylates, anhydrides (such as the anhydride prepared from 1,12-dodecanedioic acid).

Other additives that can be used in powder coatings in conjunction with the compounds of the invention include: degassing agents, flow promoters, tribo charge additives, curing catalysts, sensitizers, cationic photoinitiators and free radical photoinitiators, as well as conventional 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 and cause poor flow and degassing and reduced storage stability. This is particularly useful in formulations with high reactivity, such as the acrylic compounds functionalized with glycidyl methacrylate. Here, the combination of the compounds of the invention together with UV absorbers, especially from the class of the hydroxyphenyltriazines, can be used to improve weatherability without causing catalysis. In other binder systems and with other classes of UV absorbers, which have previously been reported to be particularly suitable for automotive coatings, synergistic weather-resistant effects have also been found.

In powder coatings, the compounds of the invention can also be used to improve oxidation stability and to reduce yellowing during curing and baking. Here, not only is the low basicity an advantage, but also the ability of the sterically hindered morpholines to resist yellowing and prevent yellowing caused by nitrogen oxides in gas fired furnaces. The use together with, in particular, phosphite and phosphonite costabilizers, as described in EP-A-816442, and dialkyl esters of dithiopropionic acid is particularly advantageous. The compounds of the invention, where appropriate, can also be used to stabilize polyesters during preparation as well as during all stages of subsequent application.

The pigments can be inorganic, organic or metal pigments. The new coating compositions preferably do not contain pigments and are used as a clear coat.

The use of the coating composition as a top coat for use in the automotive industry, in particular as a pigmented or non-pigmented top coat of the paint finish, is also preferred. However, its 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 R5, R6, R7, Rg and R, independently of one another, H, C 1 -C 8 alkyl, C3- C8 alkenyl, C5-C12 aryl, an electron withdrawing group, C6-C12 alyl substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen and wherein at least one of the groups R 5, R 6, R7, R8 and R, is not H. The present invention 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 30 and R 9 independently of one another are C 1 -C 8 alkyl, C3-C8 alkenyl, C5 -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 are as defined above.

Preferred compounds of the formula I are those of the formula 1 1 ö 9 4 56 le Ia -N-— N- = 1-

5 v Λ NrN

1 H, CJ KCH, H 3 C N X CH.

0 (la) r9 - r8 10 R? / n n L Rs7 Rs j 15 wherein the index n ranges from 1 to 15, in particular from 3-9; R5-R9 are as defined for formula I; R12 C2-C | 2 alkylene, C4-C | 2 alkenylene, C5-C7 cycloalkylene, C5-C7 cycloalkylene di (C, -C4 alkylene), C, -C4 alkylene di (C5-C7 cycloalkylene), phenylene di (C, -C4 alkylene) 20 or C4-C | 2 alkylene interrupted by 1,4-piperazinediyl, —O— or> N-X ,, where X, C | -C) is 2 acyl or (C, -C | 2 is alkoxy) carbonyl or has any of the definitions of R 14 below except hydrogen; whether R, 2 is a group of the formula (Ib ") or (Ie"); 25 -CH —CH — CH2- (Ib ') 0 c = o x2 30 10 1 13 3 4 »57 O — v / -0 - X3— <X) X3 (' <= ') 5 where m 2 or 3 X 2 is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; phenyl which is unsubstituted or substituted with 1, 2 or 3 CrC4 alkyl or CrC4 alkoxy groups; C7-C9 phenylalkyl which is unsubstituted or which is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; and the radicals X3 are independently C2 -C12 alkylene; the radicals A independently are —OR13, —N (R14) (R5) or a group of the formula (Id); H3C CH3 15, -X R. ^ / Rs -X— (N-O - 1- \ (ld ') r9 Re h3c ch3 20 R13, R14 and R | S, which are the same or different, hydrogen, C 1 -C 18 alkyl, C 5 -C 2 cycloalkyl unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C 3 -C 8 alkenyl, phenyl unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl or C 2 -C 4 alkyl are substituted 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 (le '); Ie ') X - / where Y is —O—, —CH2—, —CH2CH2— or> N-CH3, or —N (RI4) (R | 5) is further a group of formula (Ie'); / <r- s, Γ); 1 I υ. - it is 58 X —O— or> N — R, 6; R 6 hydrogen, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 2 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C7-C9 phenylalkyl which is unsubstituted or is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl, a group of the formula (ΙΓ) H, C CH3 _V R8 Rs - (Λ-ο I l ^ <R <"'> h3c ch3 R 9 10 or C2-C4 alkyl which is in the 2, 3- or 4-position is substituted with -OH, C 1 -C 8 alkoxy, di (C 1 -C 4 alkyl) amino or a group of formula (Ie ');

Rn has one of the definitions given for R16; and residues B independently have one of the definitions of A; and wherein in the individual recurring units of the formula (Ia) each of radicals B, Rn and R) 2 may have the same or different meanings.

Other new products of this method correspond to formulas IIIc, IVa and Va 20 V2 F1 N-O-C-C-CH3, (IIIc) V h2 h2 „, A« 25 3

Ri \ .R2> <_> Rs R N-O— | -1 -— R 6 (IVa) 30 R 9 R 23 R 3 ^ 4 10 1 i ··> o. Λ »59

Rl / R 2 X R8 R7 Rs R N-0 --- [- R6 (V) 5 Xn R 9 R 20 R 21 R 3 * h2 c— 10 where R is an organic linking group of the formula (VI) ;

V

E2 is —CO— or - (CH2) p—, where p is 0, 1 or 2; E, is a carbon atom containing two radicals R24 and R2J, or> N-R25, or oxygen is 15, and R24 and R25 are hydrogen or an organic radical, characterized in that the linking group R contains 2-500 carbon atoms in total and together with the carbon atoms to which it is directly bonded and the nitrogen atom forms a substituted 5, 6 or 7-membered cyclic ring structure;

Rh R2, R3 and R4 independently of one another are C, -C 8 alkyl or C, -C 5 hydroxyalkyl, or 20 R, and R 2 together with the carbon atom to which they are attached are C 5 -C 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C5 -C12 cycloalkyl;

Rs, R6, R7, Rg and Rq independently of one another H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 12 aryl, C 1 -C 4 haloalkyl, an electron withdrawing group or C6-C 2 aryl substituted with a radical selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; R20 and R2 are halogen; and R22 and R23 are hydrogen or together are a chemical bond, h2 r 4 c-30 with the proviso that R in formula IIIc is not the linking group 2, where R 2 S c-H2 R24 and R25 together = 0 or wherein R24 is hydrogen and R25 is hydrogen, OH, or alkacrylamide . ... is 60 noyloxy which is substituted with phenoxy or alkylphenoxy.

When E is substituted carbon, E2 is primarily - (CH2) p -, especially CH2; when E is oxygen or NR25, E2 is mainly carbonyl.

Thus, a compound of formula IIIc, IVa or Va is preferred, wherein 5 R is a divalent C7-C500 hydrocarbon or a C2-C500 hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen, which has the structure h2 h2 H2 C— C— 10 R * \ / C_ (Vla), R «- n '(Vlb) or O (Vic) ry ~ v

(CH2) p O O

wherein p is 0, 1 or 2; R 1, R 2, R 3 and R 4 independently of one another are C 1 -C 6 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 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C5-C) 2 cycloalkyl; R5 and R6 are independently H or methyl; and R7, Rg and R9 are independently C, -C4 haloalkyl, phenyl, vinyl, nitro, CN, COOR10, wherein R10 is C, -C12 alkyl, C5 -C2, cycloalkyl or phenyl; R24 and R25 are independently hydrogen or an organic radical as defined; and R26 is hydrogen or an organic radical, which together with the residual structure of the formula (Vlb) and is C2-C500 hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen.

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 independently are C 1 -C 4 bromoalkyl, phenyl, CN, COOR, O, wherein R 10 is C, -C 12 alkyl, C 5 -C 2 cycloalkyl or phenyl; in particular wherein R5, R6, R7, Rg and R1 are hydrogen; R20 and R2] are bromine; and | U i s O O '' v »61 when R has the structure of the formula V1a, p is 1 and Rh R2, R3 and R4 are independently methyl or ethyl; when R has the structure of the 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 1, 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C 5 -C 1 2 cycloalkyl; if R has the structure of the formula VIc,

Rh R2, R3 and R4 are independently C, -C8 alkyl or C, -C5 hydroxyalkyl, or R, and R2 together with the carbon atom to which they are attached are C5-C, 2 cycloalkyl 10, or R3 and R4 together with the carbon atom to which they are attached are C5 -C12 cycloalkyl.

Special emphasis is placed on a compound of formula IIIc r '\ / r2

15 X.

Ft NOCC — CH3, (IIIc) V h2 h2 Λ 20 where R is a C7-C500 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 5- or 6-membered cyclic ring structure, and

R1, R2, R3 and R4 are as defined above, with the proviso that R does not complete the formula IIIc so that a structure of the formula

\ y _ CH

O-7 \ N O C CH 3 H '-H 2 H 2 30 r / r 3 is formed.

1 0 1 139 4 62

A compound of the formula IIIc shown above is particularly preferred.

Thus, the new sterically hindered amine usually has the formula (1a), (1b) or (2a) or contains at least one group of the formula (3) or (4) 5 10 g-chs - ^ _ VG 'g-ch 2 J \ G 'G „G, r ^ Vo-G, 2 ^ Gn-ONU. (1b ,.

G CHi ΓΝ G-CH ^ I

L CH 'Jn, 0H3 n2 _ 15

R2 O

G. - NO (2a) R4 CH3G, CH3G, g-ch2 J-Lg2 g-ch2 ^ J-j ^ G2 G-n) <O). Gl "V N_ (4) 'G-CH ^ 1 Q ~ C" 2CH3 CH3 0M3 25 where n, is a number from 1 to 4, G and G, independently of each other are hydrogen or methyl, 30 G ,, n- propoxy, O-CH = C-CH2, O-CH = CH-CH3 or halogenated n-propoxy, especially n-propoxy, or brominated n-propoxy; G12, when η, 1 is C, -C] 8 alkyl, which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent moiety of a 10 1 1 3 G4 63 »aliphatic, cycloaliphatic unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus containing acid or a monovalent silyl residue, preferably a residue of an aliphatic carboxylic acid with 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid with 7 to 15 carbon atoms, or an α, β-unsaturated carboxylic acid with 3 up to 5 carbon atoms, each carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety, if present, may be substituted with 1 to 3 -COO 2) 2 groups, where Z | 2 H, C 1 -C 20 alkyl, C3 -C12 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl, G | 2, when n is 2, C2-C, 2 alkylene, C4-C, 2 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarb-10 amic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid of 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid of 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid of 8-14 carbon atoms, each dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety with one or two two -COOZl 2 groups may be substituted, G | 2, when n, 3, is a trivalent moiety of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which is in the aliphatic, cycloaliphatic or aromatic moiety with - COO 2, 2 may be substituted, or is from aromatic tricarbamic acid or from a phosphorus-containing acid, or is a trivalent silyl radical, 20 and G 12, when n is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; R 1, R 2, R 1 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 are cs-c12 cycloalkyl; G is hydrogen or methyl; G, and G2 are independently hydrogen or methyl or together are a substituent = 0; and G3 is a direct bond or methylene, open bonds in formulas (3) and (4) are bonded to a carbon, nitrogen or oxygen atom of an organic residue as defined above,

Gl 3 hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 5 aralkyl, C 1 -C 8 alkanoyl, C3-C5 alkenoyl, benzoyl or a group of formula (lb-1) is 101 1394 64 CH3 g G —CH ^ j / 1 5 G — CH ^ | CH3 n2 is the number 1, 2 or 3; 10 and Gl4, when n2 is 1, hydrogen, C1 -C18 alkyl, C3 -C8 alkenyl, C5 -C7 cycloalkyl, C1 -C4 alkyl which is substituted with a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula —CH 2 —CH (OH) —Z or of the formula —CONH — Z, wherein Z is hydrogen, methyl, or phenyl;

Gm, if n2 is 2, C2 -C12 alkylene, C6 -C12 arylene, xylylene, a —CH2 — CH (OH) —CH2-15 group or a —CH2 — CH (OH) —CH2 —O-D— O- group wherein D is C2-C10 alkylene, C6-C15 arylene, C6-C2 cycloalkylene or, provided G13 is not alkanoyl, alkenoyl or benzoyl, G14 also being 1-oxo-C2-C12 alkylene , a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or further the group -CO— can be 20 Gi4, if n2 is 3, a group j? CH2CH (OH) CH2- -CH2CH (OH) CH2 ^ n / ^ n /

2S O ^ N ^ O

CH2CH (OH) CH2- is 30 or, when n2 is 1, Gl3 and G4 together may be the divalent moiety of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Preferred new sterically hindered amines of the formula IIIc are as previously described in sections (b ’) - (j’) and the associated ιοί- ΐ I · 1 ·

P

65 preferences given. The new compounds of formula IIIc are useful as organic matter stabilizers against degradation by light, oxygen and / or heat. The materials to be stabilized can be, for example, oils, fats, waxes, cosmetics or biocides. Of particular interest is the application in polymer materials, such as in plastics, rubbers, coatings, photographic materials or adhesives; examples are organic polymers as described above and reprographically, in particular color photographic material, as described, for example, in GB-A-2319523, DE-A-19750906, page 23, line 20 to page 105, line 32, or in US- A-5538840, column 25, line 60 to column 10 106, line 31; these parts of US-A-5538840 are to be considered incorporated herein.

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

The invention is further illustrated in the examples below. All 15 parts or percentages are by weight unless otherwise stated in the examples as well as in the rest of the description and in the claims. Room temperature, unless otherwise stated, indicates a temperature in the range of 20-30 ° C. The following abbreviations are used in the examples: smp. melting point or range; 20 Mn number average molecular weight (g / mol);

Mw weight average molecular weight (g / mol); GPC gel permeation chromatography.

: 'i ^ ^ Q \ \ G ^

Example I: Preparation of the starting compound of the formula 66 cn N-f% -N- (CH ^ -N - Λ N We | r T T ^ ° Λ Hp ^ N CH, HjC ^^ N CHj HjC N CHj H3C N CHj

η H H H HC_N

N-C4Hg HgC, -N HsK 11 10 ^

H

15

Step 1: A solution of 74.3 g (0.35 mol) N- (2,2,6,6-tetramethyl-4-piperidinyl) -n-butylamine in 50 ml of water is slowly added to a solution of 64.5 g (0.35 mol) of cyanuric chloride in 500 ml of xylene, maintaining the temperature during the addition and for 1 hour more.

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 1/2 hour at 0 ° C and an additional 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.

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

After washing with water, the organic phase is concentrated under vacuum at 60-70 ° C / 10 mbar, 250 ml of xylene being recovered.

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 at 150 ° for 2 hours C are heated, cooled again and 14 g (0.35 mol) of ground sodium hydroxide are added.

The mixture is heated at 140 ° C for an additional 4 hours, with the remaining water of 1 µl.

The reaction azeotrope is removed and heated at 160 ° C for 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 for the isolation of the compound described in Example VI 5.

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 to 140 ° C for 3 hours and 20.3 g (0.147 mol) of ground milled potassium carbonate are added, refluxing the mixture and azeotroping the water of the reaction.

The mixture is heated at 160 ° C for 4 hours, an additional 20.3 g (0.147 mol) of ground potassium carbonate is added and heating at 160 ° C for 2 hours again. 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 with a melting range is obtained after drying at 130-136 ° C; Mn (according to GPCf: 2830 g / mol.

101 13 0 4

Example II: Method according to the present invention; preparation of the compound of the formula »68 5 H £ 4 1 μ l

"VS-" T <<> ϋ <ί ^ γ1'1 I

I γ „Λ- -Λ- I sOa I *

CJ \ ch, H3CΝch, ^ I

1 η °

10 Ο ° M 1 I Η, Ο, -N

N-C4H9 I I K, C4 Ν I I

cH, U HpjYcH, CH, ^ C.H,

Hp ^ UO \ o 15 \ CH3 20 Step 1: In a 1 liter stainless steel autoclave equipped with heating and a mechanical stirrer, a solution of 150 g (0.05 mol) of the product of Example I in 400 ml of xylene, 66.5 g (0.55 mole) of allyl bromide and 114 g (0.825 mole) of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours and then cooled to 60 ° C.

300 ml of water are added and the mixture is stirred vigorously. The organic layer is then collected and placed in a 1 liter round bottom flask equipped with a mechanical stirrer, a thermometer and a dropping funnel. After cooling to -15 ° C, 128 g of a solution of 32 wt.% Peracetic acid in acetic acid is added over 30 minutes with stirring. The temperature is raised to 0 ° C and the reaction mixture is allowed to react for 4 hours.

A solution of 250 g of K2CO3 in 500 ml of water is added and stirred at 0 ° C for 30 minutes. The organic layer is collected, washed 3 times with 10 1 13 3 4% 69 100 ml portions of water and dried over sodium sulfate.

Step 2: The solution is placed in a 1 liter stainless steel autoclave. After adding 3 g of 5 wt% platinum-on-carbon, the auto-5 claaf is filled with 40 bar of hydrogen and kept at 70 ° C with stirring for 6 hours. The autoclave is 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. 127-135 ° C, Mn (GPC) = 3580 g / mol, Mw / Mn = 1.33.

10

Example III: Method according to the present invention; preparation of the compound of the formula

15 / X

/ (20

In a round bottom flask, fill: 20 g of 1-allyl-2,2,6,6-tetramethyl-piperidin-4-ol, 40 ml of methanol, 118 g of a 35 vol% solution of H 2 O 2.

The mixture is heated to 65 ° C and allowed to react for 5 hours, then concentrated in vacuo until the methanol is distilled off and then 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, CDCl 3) / ppm: 5.90-5.80 (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).

30 101 13 9 4

Example IVa: Preparation of the compound of the formula * 70

V

5 HO- (N-O

10 To be placed in a stainless steel autoclave: 20 g of the product of Example III, 0.2 g of Raney nickel and 100 ml of toluene; the autoclave is filled with 8 bar hydrogen and kept at 25 ° C with stirring for 8 hours. The autoclave is then bled, the catalyst is removed by filtration and the mixture is concentrated in vacuo. The product is obtained as a white solid.

15 '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 IVb: Preparation of the compound of the formula A / -7 v O-N) -O O'x

V

Place in a round bottom flask: 20 g of the product of Example IVa), 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 with stirring for 6 hours, then cooled and concentrated in vacuo to give the above product as oil.

1 H-NMR (300 MHz, CDCl 3) / ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H); 1.77 (m, 101 13 ^ 4 $ 71 4H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6H).

Other Analytical Data: HPLC Assay: 80%

Elemental analysis C measured 67.6% calculated 68.4% 5 H measured 10.6% calculated 10.8% N measured 4.7% calculated 4.7%

Example V: Method according to the invention; preparation of the compound of the formula 10 \ / O. O—

V

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

The solution is filled into a round bottom flask and 8 g of metachloroperbenzoic acid dissolved in 50 ml of toluene are added over a period of 25 minutes, keeping the temperature below 25 ° C.

Then a solution of 13 g of potassium carbonate in 100 ml of water is added to the reaction mixture and stirred for 30 minutes. The organic layer is collected and washed with a potassium carbonate solution prepared as described above.

The organic layer is then dried over sodium sulfate and placed in a stainless steel autoclave.

After adding 1 g of 5 wt.% Platinum-on-carbon, the autoclave is filled with 10 1 13 9 4 72 8 bar hydrogen and stirred at 25 ° C for 4 hours. 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, 5H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6H).

Other Analytical Data: HPLC Assay 78%

Elemental analysis: C measured 67.2% calculated 68.4% H measured 10.3% calculated 10.8% 10 N measured 4.6% calculated 4.7%

Example VI: Intermediate with the formula N_ ρ * -ν — ps — ï— ™ “Γ” ΤΗ -Λ "'' I"

Kp N CH, N CHj ^ 1 1

1 1 H

H H M H

HA - N

20 CH, ψ N CH, i

H

The preparation of the present compound proceeds according to the method described in example I to step 1. The solution obtained in step 1 is then concentrated at 140 ° C and 1 mbar, yielding a solid, mp. 138-143 ° C, with an average Mn (by GPC) of 2555 g / mol is obtained.

30 1011394 73

Example VII: 5 \ ^^ 0-N- (CH ^ -N - Λ-N- (OU-N--

Hp ^ N ^ CH, H, C N CH, Η, Ο N CH,

0 0 o O

S r1 "" l S \ 10 v / Yca,

Hp ^ N ^ CH,

O

\ 15

66.5 g of allyl bromide and 114 g of potassium carbonate are added to a solution of 150 g of the product of Example VI in 400 ml of xylene. The mixture is heated to 150 ° C and allowed to react for 5 hours, after which it is cooled to 60 ° C. 300 ml of water are added and the mixture is stirred vigorously.

The organic layer is then collected and cooled to -15 ° C, after which 128 g of a 32 wt.% Solution of peracetic acid in acetic acid is added over 30 minutes with stirring. The temperature is raised to 0 ° C and the reaction mixture is allowed to react for 4 hours.

A solution of 250 g of K2CO3 in 500 ml of water is added with stirring and this is allowed to react for 30 minutes at 0 ° C. The organic layer is collected, washed 3 times with 100 ml portions of water and dried over sodium sulfate. The solution is placed in an autoclave of stainless steel with a capacity of 30 1 liter. After adding 3 g of 5 wt% platinum-on-carbon, the autclave is filled with 40 bar of hydrogen and stirred at 70 ° C for 6 hours. The autoclave is then cooled to 20 ° C and vented. After removing the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. It is obtained as a white solid, mp. 125-135 ° C, Mn (GPC) = 2979 g / mol.

Example VIII: Compound of formula 5c,

N ^ N

15 To a solution of 93 g of 2-chloro-4,6-bis (Nn-butyl-N- (2,2,6,6-tetramethyl-piperidin-4-yl)) -1,3,5-triazine in 300 ml of toluene 42 g of allyl bromide and 71.7 g of potassium carbonate are added. The mixture is heated to 150 ° C and allowed to react for 10 hours, after which it is cooled to 60 ° C and 300 ml of water is added with stirring. The organic layer is then collected and cooled to -5 ° C and 64 g of a 39% by weight solution of peracetic acid in acetic acid are added over 30 minutes with stirring. The temperature is raised 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 the mixture is stirred at 0 ° C for 30 minutes. The organic layer is collected and dried over sodium sulfate. The solution is filled in 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 stirred at 70 ° C for 6 hours. The autoclave is then cooled to 20 ° C and vented. After removing 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).

Ί 0 'i; 3 d 4

Example IX: Compound of Formula 75! X ΝΛ xx - X-7 \ n N). Ί ΑΛ <6; 6; A mixture consisting of 64.5 g of the compound described in Example VIII, 200 ml of xylene, 20.4 g of potassium carbonate and 4.6 g of Nl- [2- (3-amino-propylamino) ethyl] propane- 1,3-diamine is heated at 140 ° C for 10 hours, 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 X: Compound with the formula "\ x / / Λ 30

To a solution of 30 g of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-. P. a. · - r. 50 g of hexanediamine in 240 ml of toluene, 50 g of allyl bromide and 63 g of potassium carbonate are added. The resulting mixture is heated to 150 ° C and allowed to react for 6 hours, after which it is cooled to 20 ° C and filtered and the volume of the solution is reduced to 100 ml by evaporation of the solvent at 110 ° C and under a vacuum of 1 mbar. 150 ml of toluene are added to the concentrated solution and, after cooling to -10 ° C, a solution of 82 g of m-chloroperbenzoic acid in 200 ml of toluene is added with stirring over an hour. 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 the mixture is allowed to warm to 20 ° C.

The organic layer is collected, dried over sodium sulfate, and hydrogenated with 40 g hydrogen with 2 g 5% platinum-on-carbon at 70 ° C for 8 hours. The catalyst is recovered by filtration and the solution is concentrated at 110 ° C and 1 mbar.

15 'H NMR (300 MHz, CDCl 3) / 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 XI: Compound of the formula 20 O ^ 25

70 g of 4-bromo-2-butene and 100 g of potassium carbonate are added 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. . The mixture is heated to 140 ° C and allowed to react with stirring for 10 hours, after which it is cooled to 20 ° C, poured into 200 ml of water and stirred. The organic layer is then collected and concentrated by removing 100 ml of solvent at 110 ° C and 20 mbar, after which 100 ml of fresh toluene is added. The resulting solution is cooled to -15 [deg.] C. and a solution of 100 g of m-chloroperbenzoic acid in 200 ml of toluene is added with stirring over 30 minutes over a period of 30 minutes. The mixture is allowed to react at 0 ° C for 2 hours, after which 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 is evaporated under vacuum. The product is obtained as a pale yellow liquid.

1 H-NMR (300 MHz, CDCl 3) / 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 XII: Compound of Formula 15 | \

102 g of potassium carbonate and 135 g of propargyl bromide are added to a solution of 52 g of 2,2,6,6-tetramethylpiperidine in 250 ml of hexane. The mixture 20 is heated to 140 ° C and allowed to react for 10 hours with stirring, after which it is cooled to 20 ° C, poured into 300 ml of water and stirred. The organic layer is then collected, dried over sodium sulfate and distilled in vacuo, collecting the fraction at 64 ° C and 10 mmHg, which is then dissolved in 250 ml of dichloromethane and cooled to -15 ° C. The resulting solution is added over 30 minutes with stirring to a solution of 100 g of m-chloroperbenzoic acid in 200 ml of hexane. The mixture is allowed to react at 0 ° C for 2 hours, after which a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. The organic layer is collected and dried over sodium sulfate and the solvent is evaporated in vacuo. The product is obtained as a pale yellow liquid.

1 H-NMR (300 MHz, CDCl 3) / ppm: 6.82 (t, 1H); 5.49 (d. 2H); 1.52 (s. 6H); 1.13 (s, 12H).

1 b 's' 1 -' ♦ 78

Example XIII: Compound of the formula 1/5 (N-O /

H

A mixture of 16 g of the compound described in Example XI, 500 ml of ethanol and 0.9 g of Lindlar catalyst are placed in an autoclave. The autoclave is filled with 10 bar hydrogen and kept at 40 ° C with stirring for 6 hours, after which the autoclave is cooled to 20 ° C and vented. After removal of the catalyst by filtration, the solution is concentrated under vacuum. The resulting product is obtained as a pale yellow liquid.

15 'H NMR (300 MHz, CDCl 3) / ppm: 6.29 (d, 1H); 4.01 (m. 1H); 1.57 (d. 3H); 1.45 (m, 6H); 1.12 (s, 12H).

Example XIV: Compound of Formula 20 / ~ ((N-O ^ H ~ 25

A mixture of 38 g of the compound described in Example XI, 300 ml of toluene and 1 g of 5 wt% platinum-on-carbon are autoclaved.

The autoclave is filled with 30 bar hydrogen and kept at 40 ° C with stirring for 6 hours, after which the autoclave is cooled to 20 ° C and vented. 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, CDCl 3) / ppm: 3.69 (t, 2H); 1.45 (m, 8H); 1.15 (s, 12H); 0.92 (t, 1 0 1 i 3 egg 4 »79 3H).

Example XV: Compound of the formula 5 O o J (_ — — — - - ^ ((ch ch ch ch ^ ^ 207 207 207 207 207 207 207 207) 207 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 100 g of DBE -20 (a mixture of 75% glutaric acid dimethyl ester and 25% adipic acid dimethyl ester from DuPont USA) are dissolved in 500 ml of toluene, 2 g of lithium amide are added and refluxed for 6 hours, methanol being charged for 15 hours. reaction is formed azeotrope is distilled off, then the mixture is cooled to 20 ° C, washed with water and dried over sodium sulfate, the resulting solution is then left by the same procedure and the same stoichiometric amounts as described for the preparation of the compound of Example V reacting with allyl bromide, sodium carbonate, peracetic acid, hydrogen 20 and 5 wt% platinum on carbon 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).

Λ * t \ 1 o »· - - 80»

Example XVI: Compound of Formula 5

X * V

ίο / \

Step 1: To a solution of 64 g of 2,4,6-tris (Nn-butyl-N- (2,2,6,6-tetramethylpiperi-15-dine-4-yl)) -1,3,5-triazine 48 g of allyl bromide and 55.8 g of potassium carbonate are added in 300 ml of toluene. The mixture is heated to 150 ° C, left to react for 5 hours, cooled to 60 ° C and 300 ml of water added with stirring. The organic layer is then collected and concentrated by removing 100 ml of solvent at 110 ° C and 20 mbar, 400 ml of fresh toluene 20 is added, cooled to -5 ° C and, in 30 minutes, 57 g of a solution of 39% by weight peracetic acid in acetic acid was added. The temperature is raised to 0 ° C and the reaction mixture is allowed to react for 2 hours.

A solution of 80 g of sodium carbonate in 500 ml of water is added and the mixture is stirred at 0 ° C for 30 minutes. The organic layer is collected and dried over sodium sulfate.

Step 2: The solution is placed in a 1 liter stainless steel autoclave. After adding 2 g of 5 wt% platinum-on-carbon, the autoclave is filled with 40 bar of hydrogen and stirred at 70 ° C for 6 hours, then cooled to 20 ° C and vented. After removing 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.

101 139 4

Example XVII: Compound of Formula 81 10 '

To the solution obtained in step 1 of Example XIV, 43 g of bromine is added over 30 minutes at 25 ° C with stirring in the dark. The mixture is allowed to react for 6 hours at 25 ° C, after which it is 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 light pink solid obtained has a melting point of 106-110 ° C.

20 101 133 4

Example XVIII: Compound of Formula # 82 5 i Δ —h — Ptt-N - ^ - r-pCr "r hpj \» ï I ^ Δ ^ ^ Δ; * T ^

Crt η, οΔν 0¾ Hp N HjC N CH, HjC N CHj

10 “- <*> \ I V I I J * -N

^ J J εΔ ^

HjC N CHj

O

y.

15 Δ

2.88 g of bromine are added to the solution obtained in step 1 of Example II at 30 ° C for 30 minutes under stirring in the dark. The mixture is allowed to react for 6 hours at 25 ° C, after which it is 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 light yellow solid obtained has a melting point higher than 250 ° C (decomposition).

Bromine content: 32.1 wt% Mn (according to GPC): 2862.

25 Application examples

Example XX: Light stabilizing effect in PP bands 1 g of each compound from the list below and 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 calcium stearate are placed in a turbo mixer with 1000 g polypropylene powder with a melt flow index of 2.1 g / 10 minutes (measured at 230 ° C and 2.16 1 o 1 13 ^ 3 4 83 kg), which already contains 1 g of tris (2,4-di-tert-butylphenylphosphite) and 10.5 g of pentaerythritol tetra-kis (3- (3.5 (di-tert-butyl-4-hydroxyphenyl) propionate), mixed.

The mixture is extruded at 200-220 ° C to yield polymer granules which are then utilized using a semi-industrial type 5 plant (Leonard-Sumirago (VA) -Italy) operating under the following conditions:

extruder temperature: 210-230 ° C

temperature of the cup: 240-260 ° C

stretch ratio: 1: 6 10 are converted into stretched bands with a thickness of 50 microns and a width of 2.5 mm.

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

The residual tensile strength is measured, using a constant speed tensometer, on a sample taken after different exposure times; the exposure time (in hours) required to halve the initial tensile strength (T50) is calculated from this.

For comparison, tapes made under the same conditions as above, but to which no stabilizers of the present invention have been added, are exposed.

The results obtained are shown in the table below.

Compound according to the invention T50 (h) 25 None 340

Connection of example V 3040

Example XXI: Stabilizing effect against light in LDPE films. Each compound of the list below is introduced in a slow mixer via a master composition with LDPE pellets (Riblene FF 29, supplied by Enichem, 101 133 4 »84

Milan, Italy), characterized by a density of 0.921 g / cm3 and a melt flow index (190 ° C / 2.16 kg) of 0.60 g / 10 minutes, mixed. The master batch was previously prepared by extruding powdered LDPE and 10% by weight of the compounds from the list below.

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

The films are mounted in metal frames on white paperboard and exposed in accordance with ASTM G 26-96 in an Atlas Ci 65 Xenon Are Weather-O-Meter, at a black background temperature of 63 ° C and a continuous drying cycle.

During the exposure, the properties are periodically evaluated by measuring the carbonyl increase (iCO; increase in the carbonyl concentration) using an FT-IR spectrophotometer and testing the samples for embrittlement. The residual tensile strength of some samples is measured using a constant speed tensometer, on samples taken after different exposure times; the exposure time (in hours) required to halve the initial tensile strength (T50) is calculated from this.

The results are summarized in the following table; a low increase in the carbonyl concentration and a high T50 time indicate good stabilization.

20 Table: Increase of the carbonyl concentration (iCO) after 4760 hours exposure and T50 Compound T50 / hour iCO

0.2% of Example II> 7050 0.08

Without stabilizer 660 became brittle after 1560 hours. Example XXII: Stabilizing effect against light in LDPE films treated with a Bordeaux mixture

Each compound from the list below is in a slow mixer through a master batch of LDPE pellets (Riblene FF 29, supplied by Enichem, 30 Milan, Italy), characterized by a density of 0.921 g / cm3 and a melt flow index (190 ° C / 2.16 kg) of 0.60 g / 10 minutes, mixed.

* Π V ’'; j O - - 85

The master batch was previously prepared by extruding powdered LDPE and 10% by weight of the compounds from the list below.

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

Films for the treatment with a pesticide are stored for 24 hours in a suspension of a Bordeaux mixture (commonly 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 according to ASTM G 26-96 in an Atlas Ci 65 Xenon Are Weather-O-Meter, at a black background temperature of 63 ° C and a continuous drying cycle.

During the exposure, the properties are periodically evaluated by measuring the carbonyl increase (increase of the carbonyl concentration; iCO) using an FT-IR spectrophotometer. The results are shown in the following table.

15

Table: Increase in carbonyl concentration (iCO) after the number of hours of weathering shown

Compound iCO after 0 hours 0.15% of Example II 0 20 Without stabilizer 0

Example XXIII: Stabilizing action against light in LDPE films treated with VAPAM

Each compound from the list below is in a slow mixer through a master batch containing LDPE pellets (Riblene FF 29, supplied by Enichem, Milan, Italy), characterized by a density of 0.921 g / cm3 and a melt flow index (190 ° C / 2.16 kg) of 0.60 g / 10 minutes, mixed.

The master batch had previously been prepared by extruding powdered LDPE and 10% by weight of the compounds from the list below.

The mixture is blown extruded at 210 ° C and films are obtained with a .... . '\ Λ | U i O o »86 thickness of 150 microns.

Films for the treatment with a pesticide are made for 20 days at 30 ° C, in the presence of the vapors emitted by 2 liters of an aqueous solution containing 50% VAPAM (Baslini SpA, Treviglio / BG, Italy), which is 5 in turn is an aqueous solution of 382 g per liter of metam-sodium, which has the formula CH3-NH-CS-SNa, stored in a dryer.

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

During the exposure, the properties are periodically evaluated by measuring the carbonyl increase using an FT-IR spectrophotometer and testing the samples for embrittlement. The results are summarized in the following table; a low increase in the carbonyl concentration indicates good stabilization.

15

Table: Increase of the carbonyl concentration (iCO) after 1000 hours of exposure Compound Concentration iCO

Example II 0.2% 0.38

Without stabilizer 0, it became brittle 20

Example XXIV: Stabilizing action against light in films for greenhouses

Each compound from the list below is in a slow mixer through a master batch of LDPE pellets (Riblene FF 29, supplied by Enichem, 25 Milan, Italy), characterized by a density of 0.921 g / cm3 and a melt flow index (190 ° C / 2.16 kg) of 0.60 g / 10 minutes, mixed.

The master composition had previously been prepared by extruding powdered LDPE and 10 wt% of the sterically hindered hydroxylamine ether of the present invention (compound A) and relevant concentrations of component B (= 30 oxo and / or hydroxyl group containing metal costabilizer) and C (other costalizer; carboxylic acid salt).

1011394 87 *

The mixture is blown extruded at 210 ° C and films with a thickness of 150 microns are obtained. The films are exposed on a south-facing roof of a greenhouse in Pontecchio Marconi (Bologna-Italy). The following pesticides are used in the greenhouse: 5 VAPAM (Baslini SpA, Treviglio / BG, Italy), which in turn is an aqueous solution of 382 g per liter of metam-sodium, which has the formula CH3 — NH — CS — SNa ; SESMETRIN (Bimex SpA, Isola / VI, Italy), which is a 23.75 wt% aqueous solution of permethrin of the formula 10 H, CH,

s_ XjL

) -c-c-c-u-o-c-il

/ -Η Η H Hj I IJ I IJ

Cl 15

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

During the exposure, the properties are periodically evaluated by measuring the carbonyl increase using an FT-IR spectrophotometer. The exposure is measured in kilolangley (Klys; energy per unit area); 1100 Klys corresponds to 1 year of lighting.

Compound A Component B Ca stearate iCO after 0.4% of example II 0.2% ZnO 0.2 25 0.4% of example II 0 0 none 0 0 1 i i l ^ ~ ^ 88

Example XXV: Wood Coating a) Impregnerine: The substrate (pinewood) is impregnated using a commercially available impregnating agent ("Xylamon® Incolore" solids content 5.2% of Sepam).

The impregnating agent is applied with a brush (1 application) and allowed to dry at room temperature for 24 hours.

10 b) Top layer

A topcoat is prepared of: 73.8 parts of an alkyd resin (Jagol PS 21®, E. Jager KG), 15 0.52 parts of an anti-skinning agent (Exkin 2®, Servo Delden BV) 20.8 parts of an aliphatic hydrocarbon solvent ( Exxsol D 40®, Deutsche Exxon Chemical GmbH), 4.16 parts of a metal desiccant (Jager Antihydro - Trockner®, E. Jager KG), 0.70 parts of a PE wax, 21% in solvent (Lanco Glidd AH®, GM Langer & 20 Co.).

The top layer is stabilized with 2% UVA (compound of the formula CH-

"TO" W

M \ _ / CH, X = Z-SrSrJL ° "c» H "30 UV Absorber from Ciba Specialty Chemicals) and 1% stabilizer according to the invention, as shown in the following table.

All concentrations are weight concentrations based on solid binder.

1 Ü \ ‘^ ^» 89

The top coat is applied by brush (2 applications) to the impregnated pine wood panels and the top coating is allowed to dry at room temperature for 24 hours after each application.

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

The gloss (60 °) is measured according to DIN 67530 after every 400 hours of weathering.

An unexposed spruce panel with an unstabilized top liner is used as a reference

The results are shown in the following table.

10

Table: Gloss (60 °) after 2400 hours of exposure

Unstabilized top coat 25 2% UVA 63 2% UVA + 1% compound of Example V 86 15

Initial gloss (60 °) for all samples: 92-93

The results show that good gloss retention can be achieved with the stabilizer of the present invention.

20 1011334 t 90

Example XXVI: Stabilization of a 2-layer metallic finish

The light stabilizers to be tested are dissolved in 30 g of Solvesso®100 and tested in a clear coat with the following composition (parts by weight): 5 Synthacryl® SC 303 ° 27.51

Synthacryl® SC 3702) 23.34

Maprenal® 6503) 27.29

Butyl acetate / butanol (37/8) 4.33

Isobutanol 4.87 10 Solvesso® 1504) 2.72

Crystal Oil K-305) 8.74

Leveling aid Baysilon® MA6) 1.20 100.00 15 'Acrylic resin, ®Hoechst AG; 65% solution in xylene / butanol (26: 9) 2 Acrylic resin, Hochst AG; 75% solution in Solvesso® 1004 3 Melamine resin, ®Hoechst AG; 55% solution in isobutanol 4 mixture of aromatic hydrocarbons, boiling range: 182-203 ° C (Solvesso® 150) 20 or 161-178 ° C (Solvesso® 100); producer: ®Esso 5 mixture of aliphatic hydrocarbons, boiling range: 145-200 ° C; producer: © Shell

6 1% in Solvesso® 150; producer: ®Bayer AG

1% of the stabilizer shown in the following table and 1.5% of the UVA of Example XXV are added to the clearcoat based on the solids content of the varnish. As a comparison, a clear coat is used that does not contain light stabilizers.

The clear coat is diluted with Solvesso® 100 to spray viscosity and is sprayed on a prepared aluminum panel (®Uniprime Epoxy, silver metallic base coat), which is enamelled at 130 ° C for 30 minutes, with a dry film thickness of 40 -50 µm of the clear coat is obtained.

The samples are then placed in an Atlas Xe-Worn weatherometer (CAM

101 13 9 4 »91 180) subjected to weathering with the following cycle: 40 'UV light, 20' light with rain (front), 60 'light, 60' dark with rain (both sides), light at 70 ° C , dark at 40 ° C (filter: quartz / drill; 0.55 W / cm2 at 340 nm).

The surface gloss (20 ° gloss as defined in DIN 67530) 5 of the samples is then measured at regular intervals; high values indicate good stabilization. The results are shown in the following table.

Table:

Light stabilizer 20 ° gloss (DIN 67530) after ... hours of weathering 10 0 hours 800 hours 3200 hours

None 94 33 cracks 1% compound of Example V + 92 92 72 after 800 hours

1.5% UVA

Claims (18)

1. VI 3 P Ru, Ru and R 5, which are the same or different, hydrogen, C 1 C 3 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups ; C3 -C15 g alkenyl, phenyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; C7-C9 phenylalkyl which is unsubstituted or which is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl or C2 -C4 alkyl substituted in the 2-, 3- or 4-position with -OH, C, -C8 alkoxy, di (C, -C4 alkyljamino or a group of the formula (Ie ') ; Y ^ N- (Ie ') 1. Process for the preparation of a compound of the formula I. The method of claim 1, wherein the oxidation reaction is conducted in the presence of a solvent and an oxidant selected from oxygen, peroxides, nitrates, permanganates, chlorates. A process according to claim 1 for the preparation of a compound of the formula I by oxidation of a compound of the 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 are C 5 -C 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C 5 -C 2 cycloalkyl; R5, R6, R7, Rg and R8 independently of one another H, C 1 -C 8 alkyl, C3-C8 alkenyl, C5-C 2 aryl, an electron withdrawing group or C6-C12 aryl substituted with C 1 -C 4 alkyl C 1 -C 4 alkoxy halogen; and R is a C3-C500 hydrocarbon optionally containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, and which together with the two carbon atoms and the nitrogen atom is a substituted 6-membered cyclic ring structure forms. The process according to claim 1, wherein in the compounds of formulas 20. and II R 1, R 2, R 3 and R 4 independently of each other are preferably methyl or ethyl, R 5 and R 6 independently of each other are H or methyl and R 7, R 8 and R9 independently of one another are C | -C 4 haloalkyl, phenyl, vinyl, nitro, CN or COOR | 0, or R7 and Rg together form a chemical bond and the linking group R is a hydrocarbon or a C2-C500 hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen. 101 13 9 4 * 5 G | 3 hydrogen, C 1 -C 2 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 1 -C 8 alkanoyl, C3-C5 alkenoyl, benzoyl or a group of the formula ( lb-1) is CH3 G / ' 5 G, 2, when η, 1 is C, -C18 alkyl, which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent moiety 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 of 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid 10 of 7 to 15 carbon atoms, or an α, β-unsaturated carboxylic acid of 3 to 5 carbon atoms, any carboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety, if any, may be substituted with 1 to 3 -COO 2, 2 groups, wherein Z, 2 is H, C 1 -C 20 alkyl, C 3 -C 12 alkenyl, C 5 -C 7 cycloalkyl , phenyl or benzyl, G12, when n is 2, C 2 -C 2 alkylene, C 4 -C 12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl residue, at preferably, a moiety of an aliphatic dicarboxylic acid of 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid of 8-14 carbon atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid of 8-14 carbon atoms, wherein any dicarboxylic acid in the aliphatic, cycloaliphatic or aromatic moiety with one or two —COOZ, 2 groups may be substituted, G | 2, when n, 3, is a trivalent moiety of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which is in the aliphatic, cycloaliphatic or aromatic moiety with —COOZ12 may be substituted, or is from aromatic tricarbamic acid or from a phosphorus-containing acid, or is a trivalent silyl moiety, and G 2, when n is 4, is a tetravalent moiety of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; Rh R2, R3 and R4 are independently C, -C8 alkyl or C, -C5 hydroxyalkyl, or R, and R2 together with the carbon atom to which they are attached are C5-C12 cycloalkyl 30, or R3 and R4 together with the carbon atom to which they are attached are C5 -C12 cycloalkyl; G is hydrogen or methyl; G, and G2 are independently hydrogen or methyl or together are a substituent 101. vi b 4 = 0; and G3 is a direct bond or methylene, open bonds in formulas (3) and (4) are bonded to a carbon, nitrogen or oxygen atom of an organic residue as defined above, R26 is hydrogen or an organic residue, which together with the residual structure of the formula (VIb) and C2-C500 forms a hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen. R5, R6, R7, Rg and R9 independently of one another H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 12 aryl, C 1 -C 4 haloalkyl, an electron withdrawing group or C6-C 2 aryl which is substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; R20 and R21 are halogen; and R22 and R23 are hydrogen or together are a chemical bond, R24v. P with the proviso that R in formula IIlc is not the linking group ^ j> ys, where R 25 c— H2 5. R, R 3 R <R, \ fl, V Re r7 R5 5 R ^ N ~ 0 ---- R 6 (V) / \ R o R 20 R 21 R 3 R <where R, R ,, R2, R3 and R4, R5, R6 and R, are as defined for the formula I in claim 1, R7 and R8 H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 12 aryl, C 1 -C 4 haloalkyl, halogen, an electron withdrawing group or C 6 -C 12 aryl substituted with a moiety selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; and both R20 and R2 are either hydrogen or halogen; characterized in that a compound of the formula II, as described in claim 1, is oxidized and the resulting intermediate of the formula I is subjected to hydrogenation and / or halogenation. 5. Process for the preparation of a compound of the formula V R1 \ / R2 V Re R7 Rs R '\ / R = y Re V7 Y <N-0 - x O 10 where R 1, R 2, R 3 and R 4 are independently C 1 -C 8 alkyl or C (-C 5 hydroxyalkyl, or R 1 and R 2) together with the carbon atom to which they are attached are C5-C, 2 cycloalkyl, or R3 and R4 together with the carbon atom to which they are attached are C5-C) 2 cycloalkyl; Rs, R6, R7, Rg and R *, independently of one another H, C, -Cg alkyl, C2-Cg alkenyl, C5-C, 2 aryl, C, -C4 haloalkyl, an electron withdrawing group or C6-C12 aryl substituted with a radical selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; and R7 and Rg together can also form a chemical bond; and 20 R is an organic linking group containing 2-500 carbon atoms and together with the carbon atoms to which it is directly bonded and the nitrogen atom forms a substituted 5, 6 or 7-membered cyclic ring structure; characterized in that a compound of the formula II R1 \, R2 X R =? Γ_γ Rv N - 1- (II) X i. Rf R, where all radicals R and R, -R9 are as defined for formula I, is oxidized. 101 1394 30 6. Composition, comprising A) an organic polymer sensitive to oxidative, thermal and / or actinic degradation and B) at least one compound of the formula lila, IVa or Va 25 R '\ / B 2 r.A- ° -C - C-CH3 βΛ. 30 10 113 3 4 $ V2 R = R N — 0 I-1- R e (IVa) A composition according to claim 6, comprising as an organic polymer a thermoplastic organic polymer or a binder for a coating. 8. A composition according to claim 6 which comprises 0.1 to 10% by weight, based on the material to be stabilized, of the stabilizer of component B. 9. A composition according to claim 6, comprising a further component selected from solvents, pigments, dyes, plasticizers, antioxidants, stabilizers, thixotropics, leveling aids, other light stabilizers, metal passivating agents, phosphites and phosphonites. 10. R ”LCH3 B h3c ^ n ^ ch3 (| llb> 0 <fH2 ch2 I 2 10 G "VV ~ (1b "1) G - CHf \ ch3 n2 is the number 1, 2 or 3; 15 and G | 4, when n2 is 1, hydrogen, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted with a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl a group of the formula -CH 2 -CH (OH) -Z or of the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; G14, when n2 is 2, C2 -C12 alkylene, C6 -C2 arylene, xylylene, a —CH2 — CH (OH) —CH2-20 group or a —CH2 — CH (OH) —CH2 —O-D— O- group wherein D is C 2 -C 10 alkylene, C6-C 5 arylene, C6-C 2 cycloalkylene or, provided Gl 3 is not alkanoyl, alkenoyl or benzoyl, G 14 also being 1-oxo-C 2 -C 2 alkylene a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or further the group -CO— may be, 25 G | 4, when n2 is 3, a group O II CH3CH (OH) CH2 - CH2CH (OH) CH2 ^ sK / N N <AAo CH13CHIOHIC-10113 04 »or, when n2 is 1, G13 and G14 together may be the divalent moiety of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid. N - / wherein Y is -O-, -CH-, -CH 2 CH 2 - or> N-CH 3, or —N (R | 4) (R | 5) is further a group of the formula (Ie "); X is -O- or> N-R16; 10 -CH-CH-CH2- (Ib ') 0 c = o * 2 o-V. / —O —Xs— <X) —x3— (IC) O ———————— where m is 2 or 3, X 2 is C 1 -C 18 alkyl, C 5 -C 2 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; phenyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; C7-C9 phenylalkyl which is unsubstituted or is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; and the radicals X 3 are independently C 2 -C 12 alkylene; the radicals A independently of one another are —OR13, —N (R14) (RI5) or a group of the formula (Id "); H3C CH, A Re ij_, RS 30 - Χ- (Ν- ° Ί— "% CO / \ R R 6 H3C ch3 The composition of claim 9, which further comprises a UV absorber selected from the 2-hydroxyphenylbenzotriazoles, the 2-hydroxy-phenyl-s-triazines and the benzophenones. 15 10 R ^ N-0 ---- R 6 (Va) XR "R 20 R2, R 'R 4 15 where H 2 c— R" and R are each an organic linking group of the formula e ((VI); ΕΓ E2 is —CO— or - (CH2) p— where p is 0, 1 or 2, E is a carbon atom containing two radicals R24 and R25, or is> N-R25, or oxygen, and R24 and R2S are hydrogen or an organic radical, characterized in that the linking group R contains a total of 2-500 carbon atoms; R 1, R 2, R 1 and R 4 independently of one another are C 1 -C 6 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 C5-C12 cycloalkyl; R5, R6, R7, Rg, and R4 independently of one another H, C, -C 8 alkyl, C 2 -C 8 alkenyl, C 5 -C 2, aryl, C, -C 4 haloalkyl, an electron-xylating group, or C 6 -C 12 aryl that is substituted with a radical selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; R20 and R2I are halogen; and R22 and R23 are hydrogen or together are a chemical bond. 101 13 9 4 t 11. Compound of the formula Ia A --- N-R i2 * -N --- A 20 Ύ "Rn A A B H3C \ | ^ LCH3 B h3c · n ^ ch, o (la) R9 - Re 25 -R 7 B A R 6 R 5 30 with the index n ranging from 1 to 15; R5, R6, R7, Rg and R9 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 (2 aryl substituted with C 1 -C 4 alkyl, C - 10 1 13 9 4 C4 alkoxy, halogen; R12 C2-C12 alkylene, C4-C12 alkenylene, C5-C7 cycloalkylene, C5-C7 cycloalkylene di (C, -C4 alkylene), C, -C4 alkylene di (C5- C7 cycloalkylene), phenylene di (C 1 -C 4 alkylene) or C 4 -C 12 alkylene interrupted by 1,4-piperazinediyl, -O- or> N-X-5 where X, C, -C 12 acyl or (C, -C12 is alkoxy) carbonyl or has any of the definitions of R14 below except hydrogen, or R12 is a group of the formula (Ib ') or (Ie'); 12. A compound of the formula IIIc, IVa or Va 5 N-O-C-C-CH, (11lo) h 2 h, 3 R./X 10 R1 \ / R2 X _? » R * R NO-1-1- R, (IVa) XR r9 R- r / R4 15 r - \ / r2 X Re R7 R5 R ^ - ° H-1 - [- Re (Va) 20 r / R4 Rs R21 H2 c-25 where R is an organic linking group of the formula E (^ (VI); V is E2 —CO— or - (CH2) p— where p is 0, 1 or 2; E is a carbon atom which contains two radicals R24 and R25, or is> N-R25, or oxygen is 30, and R24 and R25 are hydrogen or an organic radical, characterized in that the linking group R contains a total of 2-500 carbon atoms and together with the carbon atoms to which it is directly bonded and the nitrogen atom forms a substituted 5, 6 or 7 membered cyclic ring structure, t 0 tiow · -. * »R 1, R 2, R 3 and R 4 independently of each other C 1 -C 6 alkyl or C 1 -C 5 is hydroxyalkyl, or R 1 and R 2 together with the carbon atom to which they are attached are C 5 -C 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C 5 -C 12 cycloalkyl; Compound according to claim 12, wherein R is a divalent C7-C500 hydrocarbon or a C2-C500 hydrocarbon containing 1-200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen and having the structure H2 H2_C-R24n> / C (V1a), R26_-N \ (Vlb) R @ mch2) - <f 25 £ O (Vic) r o where p is 0, 1 or 2; R 1, R 2, R 3 and R 4 independently of one another are C 1 -C 6 alkyl or C 1 -C 5 hydroxyalkyl, or R 3, and R 2 together with the carbon atom to which they are attached are C 5 -C 2 cycloalkyl, or R 3 and R 4 together with the carbon atom to which they are attached are C5 -C12 cycloalkyl; R5 and R6 are independently H or methyl; and R7, Rg and R9 independently are C13 -C4 haloalkyl, phenyl, vinyl, nitro, CN, COOR) O, where R10 is C, -C, 2 alkyl, C5-C, 2 cycloalkyl or is phenyl; R24 and R25 are independently hydrogen or an organic radical as defined; and 14. A compound according to claim 12 of the formulas (1a), (1b) or (2a) or containing at least one group of the formula (3) or (4)] Lc * JV. 0.3 G.-y-N) -O-G12 / V V 12 H. G '-N> -n - g14 1 (G-CH 2 I (1a> Jh- / (1b)) CH3 J n wherein 20 radicals A are independently -OR, 3, -N (R, 4) (R15) or a group of the formula (IIId); H3C CH, X ~ Y <N ~ O_H2-H2 CH3 (1 "d) h3c ch3 X -O- or> N-R16; R 6, hydrogen, C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C7-C9 phenylalkyl which is unsubstituted or is substituted on the phenyl group with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl, a group of the formula (Illf) 101 139 4 $ HX CH. λΑ - (N-oc-c-CH 3 (11f) h3c ch 3 5 or C 2 -C 4 alkyl which is substituted in the 2-, 3- or 4-position with —OH, C, -C 8 alkoxy, di ( C 1 -C 4 alkyl) amino or a group of the formula (Ie *); R, I has one of the definitions given for R 16; and the radicals B independently have one of the definitions of A; and wherein the formula (Ie ') and all other symbols are as defined in formula 11 for formula Ia. A compound according to claim 12 of the formula IHb A-F-fN'A-n-r ·· -? -I-rNy-A NVN V 15. CH3 G - CH.fl L 3 Jn, CH3 J n2 R2 o 20 G ,, - N O (2a) R4 25? H3? 1 CH3G1 g-ch2 ^ _ / g2 g-ch2 ^ 1 ^ g2 G "~ V_y <(3)" G «" Nv N— (4). G-CH2-1 ~ ^ G - CH / ^ I ° 3 CH3 CH3 1011334 30 $ where n, is a number from 1 to 4, G and G are independently hydrogen or methyl, Gj, n-propoxy, O -CH = C = CH2, O-CH = CH-CH3 or halogenated n-propoxy, especially n-propoxy, or brominated n-propoxy; R24 and R25 together are = 0 or wherein R24 is hydrogen and R25 is hydrogen, OH or alkanoyloxy substituted with phenoxy or alkylphenoxy. R 16 hydrogen, C 1 -C 9 g alkyl, C 3 -C 18 alkenyl, C 5 -C 2 cycloalkyl which is unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; C 7 -C 9 phenylalkyl which is unsubstituted or which the phenyl group is substituted with 1, 2 or 3 C 1 -C 4 alkyl groups; tetrahydrofurfuryl, a group of the formula (ΙΓ) 20 "Vb. b, r, _ ^ N_o_pE = <R ·« "·> h3c ch3 9 is 25 or C 2 -C 4 alkyl substituted 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 ' ); R ,, has one of the definitions given for R16; and the radicals B independently have one of the definitions of A. 30 Ί 0 i 'io S 4 Use of a compound of the formula la according to claim 11 and / or IIIc, IVa, Va according to claim 12 as a stabilizer for organic material against degradation by light, oxygen and / or heat. 17. Method for stabilizing an organic material against the degradation by light, oxygen and / or heat by applying a stabilizer to 20 or incorporating a stabilizer in the material, characterized in that the stabilizer is a compound with the formula Ia according to claim 11 and / or IIIc, IVa or Va according to claim 12. 18. Use of a compound of formula IIIc or Va according to claim 12 as a flame retardant for an organic polymer. 1 o 3 9 4