DE19820116A1 - New diarylbutadiene diacid compounds and use of diarylbutadienes as light stabilizers for non-living organic material - Google Patents

Abstract

4,4-Diarylbutadiene-1.1-dicarboxylic, disulfinic, disulfonic and diphosphonic alk(en)ylene ester and N,N'-alk(en)ylene-dicarbonamide compounds (IA), with the diene system in the Z,Z-, Z,E-, E,Z- or E,E-configuration or a mixture of these, are new. These new compounds have the formula (I): R<3>R<4> together = a cyclic group of formula (II); R<1>, R<2> = 1-20 carbon (C) alkyl, 1-20 C alkoxy(carbonyl), 2-20 C alkenyl, mono- or di-(1-20 C alkyl)-amino, 3-10 C cycloalk(en)yl or optionally substituted (hetero)aryl; Y<3> Y<4> = a divalent group of the formula -COO-, -CON(R<5>)- -SOO-, -SO2O- or -PO(OR<5>)O-; Z = an optionally substituted 1-5 C alkylene or 2-5 C alkenylene bridge, in which the 1 C alkylene and 2 C alkenylene bridge; or -C-Y<3>-Z-Y<4>-C- = optionally substituted 3-10 C cycloalk(en)ylidene or 6-10 C dicycloalk(en)ylidene; R<5> = hydrogen (H) or an optionally substituted 1-20 C alkyl, 3-10 C cycloalkyl or (hetero)aryl group; n, m = 0-5 The full definitions are given in the DEFINITIONS (Full Definitions) Field. Independent claims are also included for: (a) the use of (IA) and other 1,1-di-substituted 4,4-diarylbutadiene compounds (IB) of formula (I) with different R<3> and R<4> substituents as light-stabilizers and stabilizers for non-living organic material; and (b) the stabilized materials themselves.

Description

The present invention relates to the use of 4,4-diaryl butadienes as light stabilizers and stabilizers for non-le organic material, non-living organic material, which 4,4-diarylbutadiene as a light stabilizer and Stabilisa contains and new 4,4-diarylbutadienes.

Substituted 5-arylpentadienic acid esters are known from the publication US 4,950,467 as additives to compositions containing substrates protect against the effects of UV radiation, known. Be mentioned plastics as possible substrates. In the further be However, this document is only to be found in the production of compositions which protect the skin of warm-blooded against living beings against the effects of UV radiation. As such compositions are, for example, sunscreen, hair spray or lipstick formulations described. The one in this Monoaryl-substituted compounds mentioned in the patent ben, however, the disadvantage that they are not sufficiently photo-stable and therefore not sufficient long-term storage for other applications have bility.

In the German patent application 197 55 649.3 the use of 4,4-diarylbutadienes as photostable UV filters in cosmetics and pharmaceutical preparations for the protection of human skin or human hair against sun rays ben. However, there is no indication in this document that that such compounds are also used to protect non-living can use organic material.

The object of the present invention was to provide light stabilizers or Provide stabilizers that provide effective protection for non-living organic material, especially for art fabrics, plastic dispersions, lacquers or photographic emulsions sions or layers.

Accordingly, the use of 4,4-diarylbutadienes of the general formula I

in which the diene system is in the Z, Z, Z, E, E, Z, or E, E configuration or a mixture thereof and in which the variables have the following meaning:
R ¹ and R ^{2 are} each independently C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkylamino, C ₁ -C ₂₀ dialkylamino, C ₁ -C ₂₀ alkoxycarbonyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl or unsubstituted or substituted aryl or heteroaryl,
R ³ CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, SO ₂ R ⁵ , SO ₃ R ⁵ , PO (OR ⁵ ) (OR ⁶ ), C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl, C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl,
R ⁴ hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, SO ₂ R ⁵ , SO ₃ R ⁵ , PO (OR ⁵ ) (OR ⁶ ), C ₁ -C ₂₀ alkyl, C ₂ - C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl, C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl, or
R ³ and R ⁴ together with the carbon atom to which they are attached can also be a C ₃ -C ₁₀ cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ -C ₁₀ - Form bicycloalkenylidene in which up to four non-adjacent CH ₂ groups can be replaced by carbonyl groups,
R ⁵ and R ⁶ each independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, in which up to six groups CH _{2 are formed} by NH, N (C ₁ -C ₂₀ -alkyl), N (C ₆ -C ₂₀ - Aryl) and / or oxygen and / or up to six groups CH can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which chem up to two groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl) , N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ Bicycloalkyl, C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl, or
the radicals R ⁵ and R ^{6 of} the groupings CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) can also together form a C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge, which in the case of a C ₂ -alkenylene bridge can be substituted with up to two, in the remaining cases with up to four C ₁ -C ₄ alkyl groups, and in which two adjacent carbon atoms can be part of an unsubstituted or substituted fused benzene ring, or
the radical R ^{5 of} the groups CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the groups CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) of the radical R ³ can also together with the radical R ^{5 of} the groups CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the groups CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) des The rest of R ^{4 form} a C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two, in the other cases up to four C ₁ -C ₄ alkyl groups can be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring, and
n and m each independently assume values of 0, 1, 2, 3, 4 or 5
as light stabilizers and stabilizers for non-living organic material, in particular for plastics, plastics dispersions, lacquers or photographic emulsions or layers, ge found.

As C ₁ -C ₂₀ alkyl radicals for R ¹ to R ⁶ are branched or unbranched alkyl chains, such as. B. methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2nd , 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- Trimethyl propyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl called n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl.

As C ₂ -C ₂₀ alkenyl radicals for R ¹ to R ⁶ are branched or unbranched alkenyl chains, such as. B. vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1- Hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-none nyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl , 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetra decenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl , 2-Octadece nyl, 1-nonadecenyl, 2-nonadecenyl, 1-eicosenyl or 2-eicosenyl called.

As C ₃ -C ₁₀ cycloalkyl radicals for R ¹ to R ⁶ are branched or unbranched cycloalkyl chains, such as. B. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcy clypropyl, 1-methyl Called -2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.

As C ₃ -C ₁₀ cycloalkenyl radicals for R ¹ to R ⁶ are branched or unbranched cycloalkenyl chains with one or more double bonds, such as. B. cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohe xadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, 1,5-cy clooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecyl.

As C ₆ -C ₁₀ bicycloalkyl or bicycloalkenyl radicals for R ³ to R ⁶ are saturated or unsaturated C ₆ -C ₁ o bicyclic ring systems, such as. B. bicyclo [2.1.1] hexane, bicyclo [2.1.1] hex-2-ene, norbornane (bicyclo [2.2.1] heptane) or adamantane and in particular also bicyclic terpenes such as pinane, pinene, bornane and Camphor derivatives called.

As C ₁ -C ₂₀ alkoxy radicals for R ¹ and R ² are those which z. B. derived from the above-mentioned C ₁ -C ₂₀ alkyl radicals.

As C ₁ -C ₂₀ alkoxycarbonyl radicals for R ¹ and R ² come into consideration those which z. B. derive from the aforementioned C ₁ -C ₂₀ alkoxy most.

As C ₁ -C ₂₀ alkylamino and C ₁ -C ₂₀ dialkylamino radicals for R ¹ and R ² are those which z. B. derived from the above-mentioned C ₁ -C ₂₀ alkyl radicals. The alkyl radicals of the C ₁ -C ₂₀ dialkylamino radicals can be different. However, they are preferably the same.

Aryl for R ¹ to R ⁶ are aromatic rings or ring systems with 6 to 18 carbon atoms in the ring system, for example phenyl or naphthyl, which may be substituted with one or more radicals such as halogen, e.g. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, Hy droxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy can, wherein the alkyl radicals in the substituents which may be present are already mentioned among the C ₁ -C ₂₀ -alkyl radicals listed above. Optionally substituted phenyl, meth oxyphenyl and naphthyl are preferred.

Heteroaryl for R ¹ to R ⁶ are to be understood as residues, which z. B. of pyrrole, furan, thiophene, pyrazole, isoxazole, isothiazole, imidazole, 1H-1,2,3-triazole, 1H-1,2,4-triazole, pyridine, pyrazine, pyridazine, 1H-azepine, 2H- Azepine, oxazole, thiazole, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4- or 1,3,4-thiadiazole as well optionally the benzo or dibenzoa fused rings such. B. quinoline, isoquinoline, indole, benzo [b] furan (coumarone), benzo [b] thiophene (thionaphthene), carbazole, dibenzofuran, dibenzothiophene, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzoxazole Derive benzo thiazole, cinnoline, phthalazine, quinazoline, quinoxaline or phena zin and optionally with one or more Re such as halogen, z. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy may be substituted , where the alkyl substituents which may be present are already mentioned among the C ₁ -C ₂₀ -alkyl radicals listed above. In the case of the R ¹ and R ² radicals, the heteroaryl radicals can each be bonded to the benzene rings via a carbon or nitrogen atom; in the case of the R ³ to R ⁶ radicals, the bond is in each case via a carbon atom of the heteroaryl radical. In the former case, the remainder is bound via a nitrogen atom which carries a hydrogen atom in the underlying heteroaromatic.

The radicals R ³ and R ⁴ , together with the carbon atom to which they are attached and which is part of the butadiene unit, can be a C ₃ -C ₁₀ cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ - Form bicycloalkylidene or C ₆ -C ₁₀ bicycloalkenylidene, in each of which up to four non-adjacent CH ₂ groups can be replaced by carbonyl groups. C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl or C ₆ -C ₁₀ bicycloalkenyl groups, which make up the C ₃ -C ₁₀ cycloalkylidene -, C ₃ -C ₁₀ cycloalkylene nylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ -C ₁₀ bicycloalkenylidene groups can be derived have already been listed above as examples.

For the radicals R ⁵ and R ⁶ come as C ₁ -C ₂₀ alkyl, in which up to six groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to six groups CH are replaced by N, e.g. B. in question:

- (CH ₂ -CH ₂ -NY-) _p H, - (CH ₂ -CH ₂ -O-) _p H, - (CH ₂ -CH (CH ₃ ) -O-) _q H,

in which
p values of 1, 2, 3, 4, 5 or 6 and
q can have values of 1, 2, 3, 4 or 5,
r ₁ can assume values of 0, 1, 2, 3, 4 or 5, r ₂ and r ₃ can assume values of 1, 2, 3, 4 or 5 and
t ₁ can assume values of 0, 1, 2, 3 or 4, t ₂ and t ₃ can assume values of 1, 2, 3 or 4,
and still applies:

2 ≦ r ₁ + r ₂ + r ₃ ≦ 5 and 2 ≦ t ₁ + t ₂ + t ₃ ≦ 4.

Y stands for hydrogen, C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl, ie NY denotes groups NH, N (C ₁ -C ₂₀ alkyl) or N (C ₅ -C ₂₀ aryl).

For the radicals R ⁵ and R ⁶ come as C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two groups CH are replaced by N, e.g. B. in question:

in which
r ' ₁ and r' ₂ independently of one another have values of 0, 1, 2, 3, 4, 5, 6, 7 or 8 and
t ' ₁ , t' ₂ and t ' _{3 can} independently assume values of 0, 1, 2, 3, 4, 5 or 6,
and still applies:

1 ≦ r ' ₁ + r' ₂ ≦ 8 and t ' ₁ + t' ₂ + t ' ₃ ≦ 6.

Y stands for hydrogen, C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl, ie NY denotes groups NH, N (C ₁ -C ₂₀ alkyl) or N (C ₆ -C ₂₀ aryl).

Furthermore, one or more hydrogen atoms of the CH or CH ₂ groups in the ring systems shown by way of example can be replaced by C ₁ -C ₄ alkyl, the sum of the number of ring atoms and the number of carbon atoms of the alkyl groups being less than or equal to 10 is. Such optionally present C ₁ -C ₄ alkyl substituents have already been mentioned under the C ₁ -C ₂₀ alkyl radicals listed above. Methyl is preferred as the substituent.

Cycloalkyl radicals in which a CH ₂ group is replaced by NH, N (C ₁ -C ₂₀ alkyl) or N (C ₆ -C ₂₀ aryl) and in which one or more C ₁ -C ₄ alkyl substituents, preferably methyl substituents, are present, e.g. B .:

where Y is hydrogen, C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl. Examples of suitable C ₁ -C ₂₀ alkyl have already been listed above.

Examples of suitable C ₁ -C ₂₀ -alkyl in groups NY have already been listed above.

Examples of suitable C ₆ -C ₂₀ aryl in the groups NY are e.g. B. optionally with up to two C ₁ -C ₇ alkyl, with up to three C ₁ -C ₄ alkyl, with up to four C ₁ -C ₃ alkyl or with up to five methyl or ethyl radicals substituted phenyl or optionally with up to two C ₁ -C ₅ alkyl, with up to three C ₁ -C ₃ alkyl or with up to four methyl or ethyl radicals substituted naphthyl, such alkyl substituents optionally present already among the previously mentioned C ₁ -C ₂₀ alkyl radicals are mentioned.

The radicals R ⁵ and R ^{6 of} the CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) groupings can also together form a C ₂ -C ₅ alkylene bridge which is substituted by up to four C ₁ -C ₄ alkyl groups can be. Before is given here as a substituent methyl. For example, these are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -C (CH ₃ ) H-, -C (CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ - CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) - (CH ₂ ) ₃ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₃ -CH (CH ₃ ) - or -C (CH ₃ ) ₂ - (CH ₂ ) ₃ -C (CH ₃ ) ₂ -.

In the case of the grouping CONR ⁵ R ⁶ are preferably C ₄ - or C ₅ -alkylene bridges, in the case of the grouping PO (OR ⁵ ) (OR ⁶ ) C ₂ - or C ₃ -alkylene bridges.

In the case of the grouping CONR ⁵ R ⁶ , preferred radicals are, for. B .:

In the case of the grouping PO (OR ⁵ ) (OR ⁶ ) preferred residues are e.g. B .:

Furthermore, the radicals R ⁵ and R ^{6 of} the groupings CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) together can also form a C ₂ -C ₅ alkenylene bridge, which in the case of a C ₂ alkenylene bridge can contain up to two , in the case of a C ₃ -, C ₄ - or C ₅ -alkenylene bridge can be substituted with up to four C ₁ -C ₄ -alkyl groups. Methyl is preferred as the sub-substituent. For example, these are alkenylene bridges -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) - CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, - CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH ₂ -CH = CH- or -CH = CH-CH = CH-CH ₂ -.

In the case of the grouping CONR ⁵ R ⁶ as residues come into question, for. B .:

In the case of the PO (OR ⁵ ) (OR ⁶ ) grouping, residues are suitable for. B .:

Furthermore, two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring, which if necessary with one or more radicals such as halogen, for. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy may be substituted , where the alkyl radicals in the substituents which may be present are already mentioned under the C ₁ -C ₂₀ -alkyl radicals mentioned above. Together with the nitrogen atom of the Gruppie tion CONR ⁵ R ⁶ may thus, the radicals R ⁵ and R ⁶ groupings bil to which differ from the corresponding - benzo-fused, N-heterocyclic compounds derived therefrom by replacement of the hydrogen atom on the nitrogen atom - optionally substi tuted. Such connections are e.g. B. indole, 2,3-dihydroindole, tetrahydrochino lin or tetrahydroisoquinoline.

The radical R ^{5 of} the groups CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the groups CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) of the radical R ³ with the radical R ^{5 of} the groupings CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the groupings CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) of the radical R ⁴ together form a C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two, in the remaining cases with up to four C ₁ -C ₄ alkyl groups can be substituted. Methyl is preferred as the substituent. As C ₁ -C ₅ alkylene bridges come, for. B. in question -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - as well as the C ₂ -C ₅ alkyl bridges already exemplarily mentioned above. C ₂ -C ₅ alkenylene bridges have also already been listed as examples above.

This means instead of unity

in the formula I shown above also ring systems of the general formula

possible, wherein Y ³ and Y ⁴ each independently of one another a divalent group -COO-, -CON (R ⁵ ) - (or -CON (R ⁶ ) -), SOO-, -SO ₂ O-, or -PO (OR ⁵ ) O- (or -PO (OR ⁶ ) O-) and Z likewise a corresponding C ₁ -C ₅ alkylene or, which has already been mentioned as an example beforehand and is optionally substituted by C ₁ -C ₄ alkylene groups C ₂ -C ₅ alkenylene bridge corresponds.

The groups Y ³ and Y ⁴ are preferably the same. In the case of two identical groups, there are further -COO-, -CON (R ⁵ ) - (or -CON (R ⁶ ) -) or -SOO- C ₁ -, C ₂ -, C ₃ -, C ₄ - or C ₅ -alkylene or C ₂ -, C ₃ -, C ₄ - or C ₅ -alkenylene bridges, in the case of two identical groups -SO ₂ O or -PO (OR ⁵ ) O- (or -PO (OR ⁶ ) O -) preferably C ₁ -, C ₂ - or C ₃ - alkylene or C ₂ - or C ₃ -alkenylene bridge into consideration.

The ring systems preferably correspond to the formulas

in which
Y 'two identical groups -COO-, -CON (R ⁵ ) - (or -CON (R ⁶ ) -) or -SOO-,
Y '' two identical groups -SO ₂ O- or -PO (OR ⁵ ) O- (or -PO (OR ⁶ ) O-),
Z 'of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -C (CH ₃ ) H-, -C ( CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, - CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C ( CH ₃ ) -, -CH ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH ₂ -CH = CH- or -CH = CH-CH = CH-CH ₂ - and
Z '' of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -CH (CH ₃ ) - CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) - ₁ -C (CH ₃ ) = C (CH ₃ ) -, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) - or -C (CH ₃ ) ₂ -C (CH ₃ ) C (CH ₃ ) -.

The ring systems particularly preferably correspond to the formulas

Furthermore, two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring. Compounds of the formula I are suitable in which the unit = C (R ³ ) (R ⁴ ) z. B. corresponds to the following groupings:

wherein each of the benzene rings - in addition to the two oxygen - or nitrogen atoms in the 1- and 2-position - still one or more further substituents such as. B. fluorine, chlorine, bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. Two further substituents are preferred, these in turn preferably being the same. In particular, these are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino or C ₁ -C ₄ alkoxy. These substituents are preferably in the 3,6- or 4,5-position of the benzene ring. The alkyl radicals in the further substituents which may be present have already been mentioned under the C ₁ -C ₂₀ -alkyl radicals listed above.

Compounds of the formula I are preferably used in which the variables have the following meaning:
R ¹ and R ² each independently represent C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino or C ₁ -C ₁₂ dialkylamino.

R ³ means CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or Thienyl.

R ^{4 represents} hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl.

R ³ and R ⁴ together with the carbon atom to which they are attached can form a C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkyli in which up to four non-adjacent CH ₂ groups are formed by carbonyl groups can be replaced. Such C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene groups have already been discussed above.

The radicals R ⁵ and R ⁶ each independently mean what hydrogen, C ₁ -C ₁₂ alkyl, in which up to four groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to four CH groups can be replaced by N, C ₃ -C ₁₀ cycloalkyl in which up to two CH ₂ groups can be replaced by NH, N (C ₁ -C ₁₂ - Al kyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ -Bi cycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl.

For the radicals R ⁵ and R ⁶ come as C ₁ -C ₁₂ alkyl, in which up to four groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to four groups CH are replaced by N, e.g. B. in question:

- (CH ₂ -CH ₂ -NY-) _p H, - (CH ₂ -CH ₂ -O-) _p H, - (CH ₂ -CH (CH ₃ ) -O-) _q H,

in which
p values of 1, 2, 3 or 4 and
q can have values of 1, 2 or 3,
r ₁ can assume values of 0 or 1, r ₂ and r ₃ can assume values of 1 or 2 and
the following also applies:

2 ≦ r ₁ + r ₂ + r ₃ ≦ 3.

Y stands for hydrogen, C ₁ -C ₁₂ alkyl or C ₆ -C ₁₀ aryl, ie NY denotes groups NH, N (C ₁ -C ₁₂ alkyl) or N (C ₆ -C ₁₀ aryl).

For the radicals R ⁵ and R ⁶ come as C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH are substituted by N, such rings already mentioned above are also considered. However, NY in these ring systems is NH, N (C ₁ -C ₁₂ alkyl) or N (C ₆ -C ₁₀ aryl).

Furthermore, one or more hydrogen atoms of the CH or CH ₂ groups in the ring systems can be replaced by C ₁ -C ₄ alkyl, the sum of the number of ring atoms and the number of carbon atoms of the alkyl groups being less than or equal to 10. Such C ₁ -C ₄ alkyl substituents which may be present have already been mentioned under the C ₁ -C ₂₀ alkyl radicals. Preferred as a substituent is methyl.

Cycloalkyl radicals in which a CH ₂ group has been replaced by NH, N (C ₁ -C ₁₂ alkyl) or N (C ₆ -C ₁₀ aryl) and in which one or more C ₁ -C ₄ alkyl substituents, preferably methyl substituents, are present, e.g. B. the residues already listed above:

Examples of C ₁ -C ₁₂ -alkyl in question in groups NY of the radicals R ⁵ and R ⁶ have already been listed for the C ₁ -C ₂₀ -alkyl radicals.

Examples of suitable C ₆ -C ₁₀ aryl in the groups NY are e.g. B. optionally with a C ₁ -C ₄ alkyl, with up to two methyl or ethyl or with up to four methyl substituted phenyl or unsubstituted naphthyl, such optionally present C ₁ -C ₄ alkyl substituents already among those listed above C ₁ -C ₂₀ alkyl radicals are mentioned.

Examples of compounds of formula I in which R ⁵ and R ^{6 of} the grouping CONR ⁵ R ⁶ together form a C ₃ -C ₅ alkylene or C ₃ -C ₅ alkeny lenbrücke, which with C ₁ -C ₄ alkyl groups , preferably methyl groups, may be substituted have already been listed above.

Examples of additional benzannellation of such C ₃ -C ₅ alkylene or C ₃ -C ₅ alkenylene bridges were also listed above.

The radical R ^{5 of} the group CO ₂ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ^{3 can} also be used together with the radical R ^{5 of} the group CO ₂ R ⁵ or with one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ^{4 form} a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two, in the other cases with up to four C ₁ -C ₄ alkyl groups, and in which cher two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge are part of an unsubstituted or sub substituted fused benzene ring. Such resulting ring systems have also been exemplarily listed above.

Such resulting ring systems preferably correspond to the formula already shown above

which is derived from the unit = C (R ³ ) (R ⁴ ) of the formula I and in which
Y 'two identical groups -COO- or -CON (R ⁵ ) - (or -CON (R ⁶ ) -) and
Z 'of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ - C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) - or -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) speaks ent.

Such ring systems particularly preferably correspond to the formulas already shown

Furthermore, two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring. Compounds of the formula I are suitable in which the unit = C (R ³ ) (R ⁴ ) corresponds to the following groups, which have also already been shown:

where each of the benzene rings - in addition to the two oxygen or Nitrogen atoms in 1- and 2-position - one or more white can carry more substituents. Regarding possible substituents and their position in the benzene ring also applies here above Said.

n and m preferably each take values of independently 0, 1, 2 or 3.

Examples of the other preferred radicals R ¹ to R ⁶ have already been listed above.

Compounds of the formula I in which the variables have the following meaning are particularly preferably used:
R ¹ and R ² each independently represent C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ alkoxycarbonyl.

R ³ means CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ or CN.

R ⁴ means hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ or CN.

R ³ and R ⁴ together with the carbon atom to which they are attached can form a C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkyli in which up to four non-adjacent CH ₂ groups are formed by carbonyl groups can be replaced. Such C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene groups have already been discussed above.

R ⁵ and R ⁶ each independently represent hydrogen, C ₁ -C ₈ alkyl or C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH _{2 are represented} by NH, N (C ₁ -C ₈ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two CH groups can be replaced by N, C ₂ -C ₈ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl.

For the radicals R ⁵ and R ⁶ come as C ₁ -C ₈ alkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₈ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH are replaced by N, e.g. B. in question:

- (CH ₂ -CH ₂ -NY-) _p H, - (CH ₂ -CH ₂ -O-) _p H, - (CH ₂ -CH (CH ₃ ) -O-) _p H,

where p can have values of 1 or 2,

where Y is hydrogen, C ₁ -C ₈ alkyl or C ₆ -C ₁₀ aryl, ie NY denotes groups NH, N (C ₁ -C ₈ alkyl) or N (C ₆ -C ₁₀ aryl).

For the radicals R ⁵ and R ⁶ come as C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₈ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH are replaced by N, such ring systems already listed above are also considered. In these ring systems, however, NY is NH, N (C ₁ -C ₈ alkyl) or N (C ₆ -C ₁₀ aryl).

Furthermore, one or more hydrogen atoms of the CH or CH ₂ groups in the ring systems can be replaced by C ₁ -C ₄ alkyl, the sum of the number of ring atoms and the number of carbon atoms of the alkyl groups being less than or equal to 10. Such C ₁ -C ₄ alkyl substituents which may be present have already been mentioned under the C ₁ -C ₂₀ alkyl radicals. Preferred as a substituent is methyl.

Cycloalkyl radicals in which a CH ₂ group is replaced by NH, N (C ₁ -C ₈ alkyl) or N (C ₆ -C ₁₀ aryl) and in which one or more C ₁ -C ₄ -alkyl substituents, preferably methyl substituents, are present, e.g. B. the residues already listed above:

Examples of C ₁ -C ₈ -alkyl in question in the NY groups of the radicals R ⁵ and R ⁶ have already been described for the C ₁ -C ₂₀ -alkyl radicals.

Examples of suitable C ₆ -C ₁₀ aryl in the groups NY are e.g. B. optionally with a C ₁ -C ₄ alkyl, with up to two methyl or ethyl or with up to four methyl substituted phenyl or unsubstituted naphthyl, such optionally present C ₁ -C ₄ alkyl substituents already under the above ge led C ₁ -C ₂₀ alkyl radicals are called.

The radical R ^{5 of} the group CO ₂ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ³ can also together with the radical R ^{5 of} the group CO ₂ R ⁵ or with one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ^{4 form} a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two , in the other cases can be substituted with up to four C ₁ -C ₄ alkyl groups. This has also been discussed above. The statements made there and the preferences mentioned there also apply here.

n and m each independently take values of 0, 1, 2 or 3 at.

Examples of the other particularly preferred radicals R ¹ to R ⁶ have already been listed above.

Compounds of the formula I in which n and m are each 2 are preferably used. In particular, the two rests R ¹ and the two radicals R ^{2 are} each in the para and ortho position. In particular, the two radicals R ¹ and the two radicals R ² are each identical to one another.

Furthermore, preference is given to using compounds of the formula I in which n and m are each 1. The radicals R ¹ and R ² are preferably each in the para position.

Compounds of the formula I in which the radicals R ¹ and R ^{2 are} identical are also preferably used.

Furthermore, preference is given to using compounds of the formula I in which the radicals R ¹ and R ² and n and m are the same.

Compounds of the formula I are also preferably used, in which n and m are each 0.

The stabili according to the invention by the compounds of formula I Non-living organic material may still be used contain other additives, e.g. B. antioxidants, light stabilizers agents, metal deactivators, antistatic agents, flame inhibitors, pigments and fillers.

Antioxidants and light stabilizers, in addition to the compounds gen of formula I can be added, for. B. Connections based on sterically hindered phenols or sulfur or Costabilizers containing phosphorus.

Examples of such phenolic antioxidants are wise 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy benzyl) benzene, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy benzyl) isocyanurate, 1,3,5-tris- [β- (3,5-di-tert-butyl-4-hydroxy benzyl) propionylethyl] iso-cyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) -iso cyanurate and pentaerythritol tetrakis [β-3,5-di-tert-butyl-4- hydroxy-phenyl) propionate] mentioned.

Examples of phosphorus-containing antioxidants are: Tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, distearylpenta erythritol diphosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, Bis (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphite and  Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphite into consideration.

Examples of sulfur-containing antioxidants are wise dilauryl thiodipropionate, dimyristyl thiodipropionate, Distearylthiodipropionate, pentaerythritol tetrakis-β-laurylthio propionate) and pentaerythritol tetrakis - (- β-hexylthiopropionate) called. Furthermore, thiobisphenols such as 3,3'-di-tert-butyl- 4,4'-dihydroxy-2,2'-dimethyl-diphenyl sulfide can be added.

Other antioxidants and light stabilizers that work together with the compounds I according to the invention can be used are z. B. 2- (2'-Hydroxyphenyl) benzotriazoles, 2-hydroxybenzo phenones, aryl esters of hydroxybenzoic acids, α-cyanocinnamic acid derivatives, benzimidazole carboxylic acid anilides, nickel compounds or Oxalic acid dianilides.

A particularly good stabilization is obtained when ver Bonds of formula I, optionally in addition to others mentioned Additives, at least one other light stabilizer from the Compound class of sterically hindered amines in the usual Concentration is added.

As sterically hindered amines come z. B. Consider:
Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, the condensation product of 1-hydroxyethyl 2,2,6,6-tetramethyl-4-hydroxypi peridine with succinic acid, the condensation product of N, N '- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene diamine with 4th tert-octylamino 2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-th tramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6,6-th tramethylpiperidine-4 -yl) -1,2,3,4-butane-tetracarboxylic acid, 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone), the condensation products of 4-amino- 2,2,6,6-tetramethylpiperidines with tetramethylolacetylene diureas.

The compounds of the formula I given are preferably used if adding one or more of the aforementioned Addi tive and / or one or more other light stabilizers the compound class of sterically hindered amines, as light protective agents and stabilizers for plastics, plastic dis persions, varnishes or photographic emulsions or layers.

Examples of plastics which can be stabilized according to the invention by the compounds of the formula 1 are:
Polymers of mono- and diolefins, such as. B. low or high density polyethylene, polypropylene, linear polybutene-1, polyiso pren, polybutadiene and copolymers of mono- or diolefins or mixtures of the polymers mentioned,
Copolymers of mono- or diolefins with other vinyl monomers, such as. B. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers,
Polystyrene and copolymers of styrene or a-methylstyrene with dienes and / or acrylic derivatives, such as. B. styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS),
Halogen-containing polymers, such as. B. polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers,
Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles,
Polymers derived from unsaturated alcohols and amines or from their acrylic derivatives or acetals, e.g. B. polyvinyl alcohol and polyvinyl acetate and
Polyurethanes, polyamides, polyureas, polyphenylene ethers, polyesters, polycarbonates, polyoxymethylenes, polysulfones, polyether sulfones and polyether ketones.

The compounds of formula I, if appropriate, are preferred adding one or more of the aforementioned additives and / or one or more other light stabilizers from the Ver binding class of sterically hindered amines, for stabilization of polyolefins, in particular of polyethylene, of poly carbonates, of polyamides, of polyesters, of polystyrene, of ABS and used by polyurethanes. In particular, too Films made of the plastics mentioned are stabilized.

Furthermore, with the compounds of the formula I, optionally with the addition of one or more of the aforementioned additives and / or one or more further light stabilizers from the compound class of the sterically hindered amines, plastic dispersions and their film-coated plastic products can be stabilized according to the invention. The compounds I are preferably added to these dispersions after the preparation of the dispersion, if appropriate using customary dispersing aids. With appropriate substitution of the compounds I, z. B. with CO ₂ H, SO ₃ H or PO ₃ H ₂ groups (here R ³ in formula I means CO ₂ R ⁵ , SO ₃ R ⁵ or PO (OR ⁵ ) (OR ⁶ ), with R ⁵ or R ⁵ and R ⁶ being hydrogen), but it is also possible to prepare salts which, as a rule, have good solubility or divergence behavior in the dispersions.

For such plastic dispersions, among the polymers or copolymers already mentioned, there are those which can usually be present in the form of a dispersion. In particular, these are dispersions based on
Copolymers of mono- or diolefins with other vinyl monomers, such as. B. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers,
Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as. B. styrene-butadienes, styrene-acrylonitriles (SAN), styrene-ethyl methacrylates, styrene-butadiene-ethyl acrylates, styrene-acrylonitrile-methacrylates, acrylonitrile-butadiene-styrenes (ABS) or methyl methacrylate-butadiene-styrenes (MBS) or
Polymers derived from α, β-unsaturated acids and their derivatives, such as. B. polyacrylates, polymethacrylates, poly acrylamides and polyacrylonitriles.

Furthermore, given with the compounds of formula I if adding one or more of the aforementioned Addi tive and / or one or more other light stabilizers the compound class of sterically hindered amines, fiction are stabilized according to paints, especially such paints or lac cations, which are to a large extent influenced by environmental influences how exposed to sunlight and heat. These are e.g. B. Varnishes for exterior painting or industrial painting. Are further this is paints for stove enamels, especially vehicle paintwork gene.

Furthermore, fiction, with the compounds of formula I according to photographic emulsions or photographic layers be stabilized. The compounds of the formula I are used here especially as UV stabilizers and / or UV filters, which the negative influence of UV radiation on resistance and that Reduce exposure behavior of such emulsions or layers If necessary, you can also here, in addition to those for photogra  phische emulsions or layers usual components and Addi tives, also one or more of the aforementioned additives and / or one or more other light stabilizers from the compound Add the class of sterically hindered amines.

Another object of the present invention is not le organic material or are plastics, plastic dis persions, lacquers or photographic emulsions or layers, which compound or compounds of the formula I contain.

The non-living organic material or contain the plastics, plastic dispersions, lacquers or photographic emulsions or layers the compounds of the Formula I in a proportion of 0.001 to 10 wt .-%, preferably in a proportion of 0.01 to 5 wt .-%, based on the total amount made of material or plastic, plastic dispersion, lacquer or photographic emulsion or layer and stabilizer and counter if necessary, other additives.

Of course, several of the compounds I can be added ben, the previously specified proportions then natural Lich on the sum of the proportions of the added compounds of the Get Formula I.

The present application also relates to the new 4,4-diarylbutadienes of the formula Ia

in which the diene system is in the Z, Z, Z, E, E, Z, or E, E configuration or a mixture thereof and in which the variables have the following meaning:
R ¹ and R ² each independently represent C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkylamino, C ₁ -C ₂₀ dialkyl amino, C ₁ -C ₂₀ alkoxycarbonyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl or unsubstituted or substituted aryl or heteroaryl.

Y ³ and Y ⁴ each independently represent a divalent group -COO-, -CON (R ⁵ ) -, -SOO-, -SO ₂ O-, or -PO (OR ⁵ ) O-.

Z represents a C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two, in the other cases up to four, C ₁ - C ₄ alkyl groups may be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge may be part of an unsubstituted or substituted fused benzen ring.

Examples of corresponding units

have already been mentioned above.

The groups Y ³ and Y ⁴ are preferably the same. In the case of two identical groups, there are further -COO-, -CON (R ⁵ ) - or -SOO- C ₁ -, C ₂ -, C ₃ -, C ₄ - or C ₅ -alkylene- or C ₂ -, C ₃ -, C ₄ - or C ₅ -Alkeny lenbrücken, in the case of two identical groups -SO ₂ O- or -PO (OR ⁵ ) O- preferably C ₁ -, C ₂ - or C ₃ -alkylene- or C ₂ - or C ₃ - alkenylene bridge into consideration.

The ring systems preferably correspond to the formulas

in which
Y 'two identical groups -COO-, -CON (R ⁵ ) - or -SOO-,
Y '' two identical groups -SO ₂ O or -PO (OR ⁵ ) O-,
Z 'of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -C (CH ₃ ) H-, -C ( CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, - CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C ( CH ₃ ) -, -CH ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH ₂ -CH = CH- or -CH = CH-CH = CH-CH ₂ - and
Z '' of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -CH (CH ₃ ) - CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) - or -C (CH ₃ ) ₂ -C (CH ₃ ) C (CH ₃ ) -.

The ring systems particularly preferably correspond to the formulas

Furthermore, two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring. Compounds of the formula Ia in which the unit is suitable

e.g. B. corresponds to the following groupings:

wherein each of the benzene rings - in addition to the two oxygen or nitrogen atoms in the 1- and 2-position - still one or more further substituents such as. B. fluorine, chlorine, bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. Two further substituents are preferred, these in turn preferably being the same. In particular, these are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino or C ₁ -C ₄ alkoxy. These substituents are preferably in the 3,6- or 4,5-position of the benzene ring. The alkyl radicals in the further substituents which may be present have already been mentioned under the C ₁ -C ₂₀ -alkyl radicals listed above.

Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached can also be a C ₃ -C ₁₀ cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ - Form C ₁₀ bicycloalkenylidene, in which up to four non-adjacent CH ₂ groups can be replaced by carbonyl groups.

Examples were C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl or C ₆ -C ₁₀ bicycloalkenyl groups, from which the C ₃ -C ₁₀ - Cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ -C ₁₀ bicycloalkenylidene groups can be derived from, already listed above.

R ⁵ is hydrogen, C ₁ -C ₂₀ alkyl, in which up to six groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to six groups CH can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl, C ₆ -C ₁₀ -Bi cycloalkenyl or unsubstituted or substituted aryl or heteroaryl.

Examples in which R ^{5 is} C ₁ -C ₂₀ alkyl, in which up to six groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or Oxygen and / or up to six CH groups are replaced by N, or R ^{5 is} C ₃ -C ₁₀ cycloalkyl, in which up to two CH ₂ groups are replaced by NH, N (C ₁ -C ₂₀ alkyl), N ( C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two groups CH have been replaced by N have already been listed above.

n and m each independently take values of 0, 1, 2, 3, 4 or 5.

Examples of the other radicals R ¹ to R ^{6 of} the compounds Ia have already been listed above.

4,4-Diarylbutadienes of the formula Ia are further claimed in which the variables have the following meaning:
R ¹ and R ² each independently represent C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino or C ₁ -C ₁₂ dialkylamino.

Y ³ and Y ⁴ each independently represent a divalent group -COO- or -CON (R ⁵ ) -.

Z represents a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two, in the other cases up to four, C ₁ - C ₄ alkyl groups may be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge may be part of an unsubstituted or substituted fused benzen ring, or
Examples of corresponding units

have already been mentioned above.

Such resulting ring systems preferably correspond to the formula already shown above

in which
Y 'two identical groups -COO- or -CON (R ⁵ ) - and
Z 'of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ - C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) - or -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) - ent speaks .

Such ring systems particularly preferably correspond to the formulas already shown

Furthermore, two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring. Compounds of the formula Ia are suitable in which the unit —C (R ³ ) (R ⁴ ) corresponds to the following groups, which have likewise already been shown:

where each of the benzene rings - in addition to the two oxygen or Nitrogen atoms in 1- and 2-position - one or more white can carry more substituents. Regarding possible substituents and their position in the benzene ring also applies here above Said.

Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached can also form a C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in each of which up to four non-neighboring CH ₂ groups can be replaced by carbonyl groups.

For example, C ₃ -C ₁₀ cycloalkyl or C ₆ -C ₁₀ bicycloalkyl groups from which the C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene groups can be derived have already been listed above .

R ⁵ is hydrogen, C ₁ -C ₁₂ alkyl, in which up to four groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to four CH groups can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which up to two CH ₂ groups can be replaced by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ - C ₁₀ aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₁₂ alkylene, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl.

Examples in which R ^{5 is} C ₁ -C ₁₂ alkyl, in which up to four groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or Oxygen and / or up to four CH groups are replaced by N, or R ^{5 is} C ₃ -C ₁₀ -cycloalkyl, in which up to two CH ₂ groups are replaced by NH, N (C ₁ -C ₁₂ -alkyl), N ( C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH have been replaced by N have already been listed above.

n and m each independently 0, 1, 2 or 3.

Examples of the other radicals R ¹ to R ^{6 of} the preferred compounds of the formula Ia have already been listed above with the.

4,4-Diarylbutadienes of the formula Ia are further claimed in which the variables have the following meaning:
R ¹ and R ² each independently represent C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ alkoxycarbonyl.

Y ³ and Y ⁴ each independently represent a divalent group -COO- or -CON (R ⁵ ) -.

Z represents a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two, in the other cases up to four, C ₁ - C ₄ alkyl groups can be substituted.

Examples of corresponding units

have already been mentioned above.

The groups Y ³ and Y ⁴ are preferably the same. In the case of two identical groups, there are further -COO-, -CON (R ⁵ ) - or -SOO- C ₁ -, C ₂ -, C ₃ -, C ₄ - or C ₅ -alkylene- or C ₂ -, C ₃ -, C ₄ - or C ₅ -Alkeny lenbrücken, in the case of two identical groups -SO ₂ O- or -PO (OR ⁵ ) O- preferably C ₁ -, C ₂ - or C ₃ -alkylene- or C ₂ - or C ₃ - alkenylene bridge into consideration.

Such resulting ring systems preferably correspond to the formula already shown above

in which
Y 'two identical groups -COO- or -CON (R ⁵ ) - and
Z 'of a bridge -CH ₂ -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -, -C (CH ₃ ) ₂ -CH ₂ -, -C (CH ₃ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - (CH ₂ ) ₂ -C (CH ₃ ) ₂ -, -CH = CH-, -CH = C (CH ₃ ) -, -C (CH ₃ ) = C (CH ₃ ) -, -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-, -CH ₂ -CH = C (CH ₃ ) -, -CH ₂ - C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = CH-, -C (CH ₃ ) ₂ -C (CH ₃ ) = CH-, -C (CH ₃ ) ₂ -CH = C (CH ₃ ) -, -C (CH ₃ ) ₂ -C (CH ₃ ) = C (CH ₃ ) -, -CH = CH-CH = CH-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (CH ₃ ) = CH-CH = C (CH ₃ ) - or -C (CH ₃ ) = C (CH ₃ ) -C (CH ₃ ) = C (CH ₃ ) - speaks ent .

Such ring systems particularly preferably correspond to the formulas already shown

Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached can also form a C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in each of which up to four non-neighboring CH ₂ groups can be replaced by carbonyl groups.

For example, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₀ bicycloalkyl groups, from which the C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene groups can be derived, have already been listed above .

R ⁵ denotes hydrogen, C ₁ -C ₈ alkyl or C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH _{2 are represented} by NH, N (C ₁ -C ₈ alkyl), N (C ₆ -C ₁₀ - Aryl) and / or oxygen and / or up to two CH groups can be replaced by N, C ₂ -C ₈ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl.

Examples in which R ^{5 is} C ₁ -C ₈ -alkyl or C ₃ -C ₁₀ -cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₈ -alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two groups CH are replaced by N have already been listed above.

n and m each independently take values of 0, 1, 2 or 3 at.

Examples of the other radicals R ¹ to R ^{6 of} the compounds of the formula Ia have already been listed above.

Compounds of the formula Ia in which n and 2 are each are preferred. In particular, compounds are preferred in which the two radicals R ¹ and the two radicals R ^{2 are} each in the para and ortho position. In particular, the two radicals R ¹ and the two radicals R ² are each identical to one another.

Preference is further given to compounds of the formula Ia in which n and m are each 1. In particular, compounds are preferred in which the radicals R ¹ and R ^{2 are} each in the para position.

Preference is further given to compounds of the formula Ia in which the radicals R ¹ and R ^{2 are} identical.

Compounds of the formula Ia in which n and m is 0 in each case.

The compounds of formula I to be used according to the invention are advantageous according to the equation

prepared by condensation, wherein R ¹ to R ^{4 have} the meaning given in formula I. This also applies analogously to the preparation of the compounds of the formula Ia, in which case the reactant is used instead

the reactant

is to be used.

The above-mentioned condensation can be catalyzed by either base or acid. Suitable catalysts are:
tertiary amines, such as. B. pyridine, morpholine, triethylamine, triethanolamine;
secondary amines, such as. B. piperidine, dimethylamine, diethylamine;
NH ₃ , NaNH ₂ , KNH ₂ , NH ₄ OAc;
basic aluminum oxide, basic ion exchanger;
Na ₂ CO ₃ , K ₂ CO ₃ ;
acidic catalysts, such as. B. glacial acetic acid, formic acid, pro pionic acid;
HCl, H ₂ SO ₄ , HNO ₃ ;
acidic ion exchanger.

The amount of the catalysts is generally 0.1 to 50 mol%, preferably 0.5 to 20 mol%, of the amount of Al used dehydration.

Preferably one works at temperatures from 20 to 150 ° C, be especially 30 to 100 ° C, particularly preferably 40 to 80 ° C. Special Printing conditions are not required; in the the reaction is generally carried out at atmospheric pressure.

Alcohols such as. B. methanol, ethanol or isopropanol, aromatics, such as. B. toluene or xylene, coals Hydrogen, for example heptane or hexane, chlorinated Koh hydrogen, such as. B. chloroform or dichloromethane, diglyol  or tetrahydrofuran can be used. The reaction can can also be carried out without solvents.

It is also possible to start from methyl or ethyl esters chain esters by transesterification reactions in the presence of a to produce basic catalyst.

Suitable catalysts for the transesterification are:
basic alkali and alkaline earth salts, preferably those which are neither soluble in the starting materials nor in the products and can be easily separated off after the end of the reaction, particularly preferably: sodium, potassium or calcium carbonate or sodium hydrogen carbonate;
Alkaline earth oxides, preferably calcium or magnesium oxide and basic zeolites.

The amount of the catalysts is generally 1 to 80 mol%, preferably 5 to 50 mol%, of the amount of the used Esters.

The amount of alcohol used must be at least equimolar to amount of starting ester used. Quantities are preferred from 200 to 500 mol% of the alcohol used.

The methanol or ethanol formed is removed de style.

Preferably one works at temperatures from 50 to 250 ° C, be especially 60 to 150 ° C. Special conditions regarding printing are not required; in general you take the implementation at atmospheric pressure.

Inert, higher-boiling compounds such as Xylenes, but also toluene or mixtures of the alcohols used with liquid, short-chain alkanes such as hexane and heptane be set. It is preferred to work in the solvent-free alcohol used.

The transesterification can be carried out batchwise or continuously be carried out. Lei for continuous driving the reaction partners are preferably carried out via a fixed bed an insoluble base.  

In the event that R ^{3 is} different from R ⁴ , the compounds of formula I can in principle in their various geometric isomers, ie with a Z, Z; Z, E; E, Z and / or E, E-configured service system. The all-E and / or all-Z isomers are preferred as cosmetic light protection agents, and the all-E isomers are very particularly preferred.

If R ³ is R ⁴ , the CC double bond between C-3 and C-4 (in the vicinity of the diaryl system) can be in the E and / or Z configuration, preferably in the Z configuration.

Below was a comparison of the photostabilities of e 05188 00070 552 001000280000000200012000285910507700040 0002019820116 00004 05069rfin compounds to be used according to the invention (4,4-diaryl-substituted Butadienes) and compounds according to the prior art (monoaryl-substituted butadienes).

Standardized method for determining photostability

A 5% by weight alcoholic solution of the light to be tested Protective agent is applied to the. using an Eppendorf pipette (20 µl) Milled on a small glass plate. Through the estate Because of the alcohol, the solution is evenly distributed on the roughened glass surface. During the examination, 4 Irradiated glass plates. The evaporation time and the irradiation wear 30 minutes each. The glass plates are during the loading radiate through a water cooling system located at the bottom of the testge located, slightly chilled. The temperature within the test device is 40 ° C during irradiation. After the samples have been irradiated with ethanol in a dark Washed 50 ml volumetric flask and measured with the photometer. The Blank samples are also applied to glass slides and 30 Evaporated for minutes at room temperature. Like the other samples they are washed with ethanol and diluted to 100 ml and measured.

Comparative tests regarding photostability example 1

The following two connections were made regarding their Comparison of photostability.  

Example 2

The following two connections were made regarding their Comparison of photostability.

The percentages indicate what proportion of the corresponding Connection is still present after irradiation.

Manufacturing examples

Compounds 1 to 19 in Table 1 below were synthesized according to the following preparation instructions. In formula I, n and m are equal to 0 for all compounds. The “*” in Table 1 denotes that carbon atom which is part of the butadiene unit of the formula I. λ _max denotes the wavelength (in nm) of the maximum extinction of the corresponding compound.

Manufacturing instructions for compounds 1 to 17

Compound 1 of Table 1 was obtained as follows:
0.1 mol of β-phenylcinnamaldehyde and 0.1 mol of diethyl malonate are dissolved in 100 ml of ethanol, 1 ml of piperidine and ice sig are added and the mixture is heated to reflux for 5 h. The mixture is then diluted with water and cooled to 0 ° C., the product crystallizing out. It is dried in vacuo and 29.5 g (85% of theory) of compound 1 are obtained as light yellow crystals. Purity: <99% (GC).

Compounds 2 to 17 were obtained analogously.

Manufacturing instructions for connections 18 and 19

Compound 19 of Table 1 was obtained as follows:
0.1 mol of KOH are added to 0.1 mol of camphor in 40 ml of xylene and the mixture is heated to reflux. A solution of 0.105 mol of β-phenylcinnamaldehyde in xylene is then slowly added dropwise over 6 h. After cooling to room temperature, water is added, the organic phase is washed twice with water and then dried over sodium sulfate. After removing the solvent, the oily residue is crystallized from methanol / water. 22 g (64%) of colorless crystals of compound 19 are obtained. Purity 99% (HPLC, isomer mixture).

Compound 18 in Table 1 was obtained analogously.

Table 1

Stabilization of polystyrene

To assess the stabilizing effect, 0.2% by weight of the Compound 1 of Table 1 in polystyrene 168 N (from BASF shares company, Ludwigshafen). This will be the polysty Rol granules with the stabilizer in a glass bottle by Rol len pre-mixed on a trundle bed and then over a Single screw extruder dissolved at a melt temperature of 200 ° C and granulated. From the stabilized granules obtained the test specimen rectangular using an injection molding machine at 200 ° C with the dimensions 60 mm × 45 mm × 2 mm. According to him follows the production of an unstabilized, one with Uvinul® 3008 stabilized and one test stabilized with Tinuvin® P. body.

The test specimens are placed in a rapid weathering device WOM CI 65 (Atlas & Co., Chicago) for up to 1500 hours tet. The photodegradation of the test specimens, and associated with them increasing discoloration (yellowing), is colorimetric by means of of the yellowness indices given in Table 2 for the given weathering times determined.

Table 2

Claims (10)

1. Use of 4,4-diarylbutadienes of the formula I.
in which the diene system is in the Z, Z, Z, E, E, Z, or E, E configuration or a mixture thereof and in which the radicals have the following meaning:
R ¹ and R ^{2 are} each independently of one another C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkylamino, C ₁ -C ₂₀ dialkylamino, C ₁ -C ₂₀ alkoxycarbonyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl or unsubstituted or substituted aryl or heteroaryl,
R ³ CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, SO ₂ R ⁵ , SO ₃ R ⁵ , PO (OR ⁵ ) (OR ⁶ ), C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ Alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl, C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl,
R ⁴ hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ ₁ CN, SO ₂ R ⁵ , SO ₃ R ⁵ , PO (OR ⁵ ) (OR ⁶ ), C ₁ -C ₂₀ alkyl, C ₂ - C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl, C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl, or
R ³ and R ⁴ together with the carbon atom to which they are attached form a C ₃ -C ₁₀ cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ -C ₁₀ bicycloalkenylidene, in which up to four non-adjacent CH ₂ groups can be replaced by carbonyl groups,
R ⁵ and R ⁶ each independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, in which up to six groups CH _{2 are represented} by NH, N (C ₁ -C ₂₀ -alkyl), N (C ₆ -C ₂₀ -aryl) and / or oxygen and / or up to six groups CH can be replaced by N, C ₃ -C ₁₀ cycloalkyl in which up to two groups CH _{2 can be} replaced by NH, N (C ₁ -C ₂₀ alkyl), N ( C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkenyl, C ₆ -C ₁₀ bicycloalkyl , C ₆ -C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl, or
the radicals R ⁵ and R ^{6 of} the groupings CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) together form a C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge, which in the case of a C ₂ - Alkeny lenbrücke can be substituted with up to two, in the other cases with up to four C ₁ -C ₄ alkyl groups, and in which two adjacent carbon atoms can be part of an unsubstituted or substituted fused benzene ring, or
the R ⁵ group of the CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ^{5 group} or one of the R ⁵ or R ⁶ group of the CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) group of the R ^{3 group} forms with the radical R ^{5 of} the groupings CO ₂ R ⁵ , SO ₂ R ⁵ or SO ₃ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the groupings CONR ⁵ R ⁶ or PO (OR ⁵ ) (OR ⁶ ) of the radical R ⁴ together a C ₁ -C ₅ alkylene or C ₂ -C ₅ alkeny lenbrücke, which in the case of a C ₁ alkylene or C ₂ -Al kenylene bridge with up to two, in the other cases with up to four C ₁ -C ₄ alkyl groups may be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge may be part of an unsubstituted or substituted fused benzene ring, and
n and m each independently of one another 0, 1, 2, 3, 4 or 5,
as light stabilizers and stabilizers for non-living organic material. 2. Use of compounds of formula I according to claim 1, in which the variables have the following meaning:
R ¹ and R ^{2 are} each, independently of one another, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino or C ₁ -C ₁₂ dialkylamino,
R ³ CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl ,
R ^{4 is} hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ , CN, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl, or
R ³ and R ⁴ together with the carbon atom to which they are attached form a C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in which up to four non-adjacent CH ₂ groups are replaced by carbonyl groups could be,
R ⁵ and R ⁶ each independently of one another are hydrogen, C ₁ -C ₁₂ -alkyl, in which up to four groups CH _{2 are represented} by NH, N (C ₁ -C ₁₂ -alkyl), N (C ₆ -C ₁₀ -aryl) and / or oxygen and / or up to four CH groups can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which up to two CH ₂ groups can be replaced by NH, N (C ₁ -C ₁₂ alkyl), N ( C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two CH groups can be replaced by N, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl, or
the radicals R ⁵ and R ^{6 of} the group CONR ⁵ R ⁶ together form a C ₃ -C ₅ alkylene or C ₃ -C ₅ alkenylene bridge, which can be substituted with up to four C ₁ -C ₄ alkyl groups and in which two adjacent carbon atoms can be part of an unsubstituted or substituted anellated benzene ring, or
the radical R ^{5 of} the group CO ₂ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ³ forms with the radical R ^{5 of} the group CO ₂ R ⁵ or with one of the radicals R ⁵ or R ^{6 of} the grouping CONR ⁵ R ^{6 of} the radical R ^{4 together} form a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two , in the other cases can be substituted with up to four C ₁ -C ₄ alkyl groups, and in which two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge form part of an unsubstituted or substituted fused benzene ring can be, and
n and m each independently 0, 1, 2 or 3. 3. Use of compounds of formula I according to claim 1, in which the variables have the following meaning:
R ¹ and R ^{2 are} each independently of one another C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ alkoxycarbonyl;
R ³ CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ or CN,
R ^{4 is} hydrogen, CO ₂ R ⁵ , COR ⁵ , CONR ⁵ R ⁶ or CN, or
R ³ and R ⁴ together with the carbon atom to which they are attached form a C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in each of which up to four non-adjacent CH ₂ groups are replaced by carbonyl groups could be,
R ⁵ and R ⁶ each independently of one another are hydrogen, C ₁ -C ₈ -alkyl or C ₃ -C ₁₀ -cycloalkyl, in which up to two groups CH _{2 are represented} by NH, N (C ₁ -C ₈ -alkyl), N ( C ₆ -C ₁₀ aryl) and / or oxygen and / or up to two CH groups can be replaced by N, C ₂ -C ₈ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, or
the radical R ^{5 of} the group CO ₂ R ⁵ or one of the radicals R ⁵ or R ^{6 of} the group CONR ⁵ R ^{6 of} the radical R ³ forms with the radical R ^{5 of} the group CO ₂ R ⁵ or with one of the radicals R ⁵ or R ^{6 of} the grouping CONR ⁵ R ^{6 of} the radical R ^{4 together} form a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge which, in the case of a C ₁ alkylene or C ₂ alkenylene bridge, has up to two , in the other cases can be substituted with up to four C ₁ -C ₄ alkyl groups, and
n and m each independently 0, 1, 2 or 3. 4. Use of compounds of formula I according to claims 1 to 3 as light stabilizers and stabilizers for art fabrics, plastic dispersions, lacquers or photographic Emulsions or layers. 5. Non-living organic material containing compounds of formula I according to claims 1 to 3 as a sunscreen tel and stabilizers.   6. Plastics, plastic dispersions, lacquers and photographi emulsions or layers containing compounds of Formula I according to claims 1 to 3 as a light stabilizer and stabilizers. 7. Materials according to claims 5 or 6, containing 0.01 to 5 wt .-% (based on the total amount of material and Compounds of formula I) from compounds of formula I. 8. 4,4-Diarylbutadienes of the formula Ia
in which the diene system exists in the Z, Z, Z, E, E, Z, or E, E configuration or a mixture thereof and in which the variables have the following meaning:
R ¹ and R ^{2 are} each independently of one another C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkylamino, C ₁ -C ₂₀ dialkylamino, C ₁ -C ₂₀ alkoxycarbonyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl or unsubstituted or substituted aryl or heteroaryl,
Y ³ and Y ⁴ each independently represent a divalent group -COO-, -CON (R ⁵ ) -, -SOO-, -SO ₂ O-, or -PO (OR ⁵ ) O-,
Z is a C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two, in the other cases with up to four C ₁ -C ₄ -Alkyl groups can be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₅ alkylene or C ₂ -C ₅ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring, or
Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached form a C ₃ -C ₁₀ cycloalkylidene, C ₃ -C ₁₀ cycloalkenylidene, C ₆ -C ₁₀ bicycloalkylidene or C ₆ -C ₁₀ - Bicycloalkenylidene, in which up to four non-adjacent CH ₂ groups can be replaced by carbonyl groups,
R ^{5 is} hydrogen, C ₁ -C ₂₀ alkyl, in which up to six groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to six groups CH can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₂₀ alkyl), N (C ₆ -C ₂₀ aryl) and / or oxygen and / or up to two CH groups can be replaced by N, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkylene, C ₆ -C ₁₀ bicycloalkyl, C ₆ - C ₁₀ bicycloalkenyl or unsubstituted or substituted aryl or heteroaryl, and
n and m are each independently 0, 1, 2, 3, 4 or 5. 9. 4,4-Diarylbutadienes of the formula Ia, in which the variables have the following meaning:
R ¹ and R ^{2 are} each, independently of one another, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino or C ₁ -C ₁₂ dialkylamino,
Y ³ and Y ⁴ each independently represent a divalent group -COO- or -CON (R ⁵ ) -,
Z is a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two, in the other cases with up to four C ₁ -C ₄ -Alkyl groups can be substituted, and in which two adjacent carbon atoms of the C ₂ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge can be part of an unsubstituted or substituted fused benzene ring, or
Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached form a C ₃ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in each of which up to four non-adjacent CH ₂ groups are formed by carbonyl groups he can be put
R ^{5 is} hydrogen, C ₁ -C ₁₂ alkyl, in which up to four groups CH _{2 are formed} by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ aryl) and / or oxygen and / or up to four groups CH can be replaced by N, C ₃ -C ₁₀ cycloalkyl, in which up to two groups CH ₂ by NH, N (C ₁ -C ₁₂ alkyl), N (C ₆ -C ₁₀ Aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, naphthyl or thienyl, and
n and m each independently 0, 1, 2 or 3. 10. 4,4-diarylbutadienes of the formula Ia, in which the variables have the following meaning:
R ¹ and R ^{2 are} each independently of one another C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ alkoxycarbonyl,
Y ³ and Y ⁴ each independently represent a divalent group -COO- or -CON (R ⁵ ) -,
Z is a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene bridge, which in the case of a C ₁ alkylene or C ₂ alkenylene bridge with up to two, in the other cases with up to four C ₁ -C ₄ -Alkyl groups can be substituted, or
Y ³ , Y ⁴ and Z together with the carbon atom to which they are attached form a C ₅ -C ₁₀ cycloalkylidene or C ₆ -C ₁₀ bicycloalkylidene, in each of which up to four non-adjacent CH ₂ groups are formed by carbonyl groups he can be put
R ^{5 is} hydrogen, C ₁ -C ₈ alkyl or C ₃ -C ₁₀ cycloalkyl, in which chem up to two groups CH ₂ by NH, N (C ₁ -C ₈ alkyl), N (C ₆ -C ₁₀ Aryl) and / or oxygen and / or up to two groups CH can be replaced by N, C ₂ -C ₈ alkenyl, C ₆ -C ₁₀ bicycloalkyl or unsubstituted or substituted phenyl, and
n and m each independently 0, 1, 2 or 3.