NL9300336A - CARBONIC ACID ESTERS OF HYDROXYPHENYL ALKANOLS AS STABILIZERS. - Google Patents

Description

Carboxylic acid esters of hydroxylphenalcohols as stabilizers

The present invention relates to new carboxylic acid esters of co- (315-dialkyl-4-hydroxyphenyl) -alkanols, the organic materials stabilized with these compounds against thermal, oxidative and actinic degradation, the use of the new compounds as stabilizers, as well as new co - (3,5-dialkyl-4-hydroxyphenyl) alkanols.

The use of the esters of co-hydroxyphenyl-α-carboxylic acid esters as stabilizers for organic materials is known.

A series of publications relate to the corresponding inverse esters: GB-A-1,504,573. DE-A-2,147,544, EP-B-171,139, EP-A-349.38O, NL-A-79.05000, GB-A-1,509,876, Chem. Abstr. £ 4 106614c,

Chem. Abstr. 106 I56OOIU, US-A-4,910,286, US-A-4.3H.637. US-A-4,104,252 and US-A-3,919,097 describe carboxylic acid esters of 3 "(3.5" di-tert-butyl-4-hydroxyphenyl) -alkane-1-ols, 3 "(3-tert-butyl-5) methyl 4-hydroxyphenyl-alkane-1-ols and separate 4- (3,5-dialkyl-4-hydroxyphenyl) -alkane-1-ols, and their use as stabilizers for polymers.

Some new carboxylic acid esters of C0- (3'5 'dialkyl-4-hydroxyphenyl) -alkanols have now been found which have particularly good stabilizing properties.

Thus, an object of the present invention are compounds of the formula 1 of the formula sheet wherein n represents an integer in the range of 4 to 8 and m represents an integer in the range of 1 to 4; A in the case where m = 1 is alkyl which is unsubstituted or substituted with C 5 -C 8 cycloalkyl; or C 2 -C 25 alkyl interrupted with C 5 -C 8 cycloalkyl or one or more of the groups -S-, -O- and / or -NR 2 -; or A in the case where m = 1 C5 -C8 cycloalkyl, which is unsubstituted or substituted by C1 -C12 alkyl or C2 -C12 alkenyl; C8-C8 cycloalkenyl, which is unsubstituted or substituted with Cx-C12 alkyl or C2-C12 alkenyl; phenyl which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; naphthyl, which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; biphenyl, which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; or C2-C25alkenyl; C6-C10 bicycloalkenyl; C7-C12 phenylalkyl; C8-C12 phenylalkenyl;

C 1 -C 6 naphthylalkyl; C11 -C16 naphthylalkenyl; C12 -C18 biphenylalkyl; C13 -C18 biphenylalkenyl; or represents a group of the formula 2 of the formula sheet; A in case m = 2 a direct bond; C1-C12alkylene; C2-C12alkenylene; C5-C8 cycloalkene which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C6-C8 cycloalkenylene, which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C6-C10 bicycloalkenylene; phenylene; naphthylene; a divalent heterocyclic radical from the group furan, thiophene or pyrrole which is saturated on the nitrogen atom by hydrogen or the -R 2 substituent; or A, in the case where m = 2, is C2 -C3 alkylene interrupted by C5 -C8 cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR2-; A in the case where m = 3 C 1 -C 8 alkanetriyl; C2 -C8 olefin triyl; benzenetriyl; naphthalene triyl; a trivalent group with the formula

or C2 -C18 represents alkanedriyl interrupted by at least one of the groups -S-, -O- or -NR2-; A in the case where m = 4 is a benzene; naphthyl; tetrahydrofuryl or cyclohexyl radical with 4 free valencies; R 1 and R 1 'independently represent alkyl or C 5 -C 8 cycloalkyl; R2 represents H or C1 -C1 alkyl; R 3 and R 4 independently of one another are C 1 -C 15 alkyl; and R5, R6 and R7 independently represent C1 -C1 alkylene.

For example, R1 and R1 as C1-C21 alkyl or C5-C8 cycloalkyl independently represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl for.

Preferably Rr is secondary or tertiary C3-C10 alkyl, for example 2-butyl, (sec-butyl), tert-butyl, 2-pentyl, 2-hexyl or 3-hexyl or Rr is C5-Cg cycloalkyl, for example cyclohexyl and R1 C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl.

Particularly preferred R1 'has the meaning secondary or tertiary C3-C18 alkyl or C5-C8 cycloalkyl, for example isopropyl, sec-butyl, tert-butyl or cyclohexyl, and R1 means C3-C8 alkyl or C5-C8 cycloalkyl or meaning methyl. Particular preference is given to compounds of the formula I of the formula sheet, wherein R 1 represents methyl, tert-butyl or cyclohexyl, in particular methyl, and R 1 represents tert-butyl or cyclohexyl, especially tert-butyl.

R2, R3 and RA as C 1 -C *, alkyl mean methyl, ethyl, 1-propyl (n-propyl), 2-propyl (isopropyl), 1-butyl (n-butyl), 2-butyl (sec-butyl ), 2-methylpropyl (isobutyl) or 1,1-dimethylethyl (tert-butyl), preferably methyl or tert-butyl.

R5, R6 and R7 as alkylene are methylene, 1,1- or 1,2-ethylene, or 1,1-, 1,2-2,2 or 1,3-propylene. Methylene is preferred.

If AC is -C 1 alkyl, then it is a branched or unbranched residue, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n- pentyl, isopenyl, 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-methyl undecyl, dodecyl, 1,1,3,3,5,5-hexamethyl-hexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl or pentacosyl, alkyl is preferred, especially preferably straight chain C 8 -C 18 alkyl.

A as C 5 -C 8 cycloalkyl substituted C 1 -C 8 alkyl is, for example, cyclopentylmethyl, ceclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclohexylethyl, 2-cyclohexyl-n-propyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n.

A as C 2 -C 25 alkyl interrupted by C 5 -C 8 cycloalkyl or one or more of the groups -S-, -O-and / or -NR 2 - means one of the alkyl radicals described above with the exception of methyl, in the chain of which a place cyclopentylene or pentylidene, cyclohexylene or hexylidene, cycloheptylene or heptylidene, cyclooctylene or octylidene, or in one or more places the above groups having heteroatoms have been used. A for example corresponds to the formula 3 of the formula sheet.

A as C5-C8 cycloalkyl or Cg-C8 cycloalkeyl which is unsubstituted or substituted by C1-C12 alkyl or C2-C12 alkenyl can be, for example: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2- or 4-methylcylohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, 2-cyclohexenyl, 3 ”cycloheptenyl, cyclooctatetraenyl, 4-tert-butyl-cyclohex-2-enyl. Preference is given to cyclohexyl and cyclohexenyl, in particular cyclohexyl.

A as phenyl, naphthyl, or biphenyl substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl includes methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, vinylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, methyl -di-tert-butylphenyl, 1,1,3,3-tetramethyl-butylphenyl and 1,1,3,3,5,5 "hexamethylhexylphenyl, dodecenylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-ethylnaphthyl, 2-propyl-biphenyl -4-yl, 4- (1-hex-3-enyl) -biphenyl-8-yl Preferred here is phenyl, optionally with 1-3, for example 1-2, in particular 1 C1-C1, alkyl group (s), especially methyl, is substituted.

A as C2-C25 alkenyl means e.g. vinyl, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl. n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl, n- octadec-4-enyl.

A as C7-C12 phenylalkyl, C7-Cl2 phenylalkenyl, Cn-Cl6 naphthylalkyl, Cn-Cl6 naphthylalkenyl, C13-Cl8 biphenylalkyl or C13-Cl8 biphenylalkenyl meaning ¢ ^ - (¼ alkyl or Cj-C8 alkenyl, which with phenyl, nyl biphenyl is substituted, such as, for example, benzyl, phenethyl, 3 "phenylpropyl, α-methylbenzyl, α, α-dimethylbenzyl, 2-phenylethenyl, 1-phenylprop-2-enyl, 6-phenylhexyl, 1-naphthylmethyl-2-naphthylmethyl, 1- naphthyleth-1-yl, 2- (4-biphenylyl) -prop-2-yl, 1- (4-biphenyl) -pent-3-en-1-yl.

A as C6-C10 bicycloalkenyl or C8-C10 bicycloalkenylene is an unsaturated bicyclic, monovalent or divalent radical having 6 to 10 carbon atoms, which as a monovalent radical is, for example, bicyclo (2,2,1) -hepta-5-en-2 - yl, as bivalent residue e.g. can correspond to formulas 4 or 5 of the formula sheet.

The divalent (for m = 2), trivalent (for m = 3) and tetravalent residues A (for m = 4) are derived from the above monovalent residues. A bivalent residue differs from the corresponding monovalent residue in that it contains an open bond in place of a hydrogen atom; a trivalent residue differs from the corresponding monovalent residue. in that it contains two open bonds in place of two hydrogen atoms; a tetravalent residue differs from the corresponding monovalent residue in that it contains three open bonds at a position of three hydrogen atoms. For example, A may also be methylene, ethylene, -CH2-C (CH3) 2-CH2-, prop-2-en-ylidene, propylene (1,3) as bivalent residue within the scope of the indicated meanings. butylene (1,4), pentylene (1,5), hexylene (1,6), o-, m- or p-phenylene, compound of the formula 6 of the formula sheet, compound of the formula 7 of the formula sheet -Cyfy-S-Cyi ^ - or -C ^ -O-CH ^ -, as trivalent residue for example -CH2 -OH-CH2-, compound of the formula 8 of the formula sheet, compound of the formula 9 of the formula sheet, or compound of the formula 10 of the formula sheet, as tetravelent residue e.g. represent compounds of formulas 11, 12 or 13 of the formula sheet.

The new esters of the formula 1 of the formula sheet can be prepared according to

known esterification or transesterification methods from ω-hydroxyphenylalkanols of the formula l4 of the formula sheet and organic carboxylic acids of the formula V

(V) or derivatives of such carboxylic acids are prepared, for example, by methods such as those described in Tetrahedron 3> 2409 (1980). The symbols R1, R1 ', A, n and m in the formula 14 of the formula sheet and formula V have the meanings indicated above for formula 1 of the formula sheet. Suitable carboxylic acid derivatives are, for example, anhydrides, chlorides or lower alkyl esters, for example methyl or ethyl esters. In these syntheses, suitable esterification catalysts, such as inorganic acids (e.g. sulfuric acid) or sulfonic acids (e.g. p-toluenesulfonic acid) may optionally be used.

The reaction can be carried out in a manner known per se, expediently by adding one of the two starting materials to the second starting material and mixing the two reactants together, preferably with the exclusion of oxygen. The reaction can be carried out in the presence of a solvent, for example toluene, but also without a solvent. The temperature control is not critical, the temperature may be between the melting point and the boiling point of the reaction mixture, for example between -50 and 100 ° C, preferably between 0 and 50 ° C. The purification of the product obtained can also be carried out by known methods, for example by washing with water / HCl, extraction with an organic solvent, crystallization and / or chromatography. As the solvent for the extraction as well as for the chromatographic purification step, hexane, ethyl acetate or mixtures thereof are preferably used.

When the acid chloride is used as a derivative of the carboxylic acid of the formula V in the reaction, an acid acceptor is preferably added to the reaction mixture. As such, for example, amines such as pyridine or triethylamine are suitable. Preferably, the amount of the acid acceptor is at least equivalent to the amount of the acid chloride, for example it is 1 to 2 equivalents, in particular 1.2 to 1.7 equivalents, based on the acid chloride.

When the reaction is carried out as a transesterification of an alcohol of the formula 14 of the formula sheet with the ester of a carboxylic acid of the formula V, efficient transesterification catalysts are conveniently added to the reaction mixture. These are, for example, organic or inorganic bases (e.g. lithium amide, lithium methoxide, potassium hydroxide, etc.) or Lewis acids (e.g. dibutyltin oxide),

When the carboxylic acid of the formula V and the alcohol of the formula 14 of the formula sheet are used directly as starting materials, the reaction is preferably carried out using a water separator, distilling off water and / or using reagents which absorb released water, such as, for example, dicyclohexylcarbodiimide.

Of particular practical significance in the preparation of compounds of the formula I of the formula sheet may be the use of mixtures of carboxylic acids of the formula V or its derivatives. Such mixtures can be used for the synthesis as described above, whereby corresponding mixtures of compounds of the formula I of the formula sheet are obtained. Mixture of compounds of the formula I of the formula sheet can be used as stabilizers per se.

Alcohols of the formula 14 of the formula sheet already act as stabilizers themselves. Compositions containing (a) an organic material sensitive to oxidative, thermal and / or actinic degradation and (b) a compound of the formula 14 of the formula sheet, as well as the use of compounds of the formula 14 of the formula sheet for stabilizing organic matter against oxidative, thermal or actinic degradation are therefore further objects of the invention.

The compositions of the invention preferably contain those compounds of formula 14 of the formula sheet wherein R 1 means secondary or tertiary C 3 -C 10 alkyl or C 5 -C 8 cycloalkyl; and R 1 has the meaning of C 1 -C 10 alkyl or C 5 -C 18 cycloalkyl. Particularly preferred R1 'has the meaning secondary or tertiary C3 -C18 alkyl or C5 -C8 cycloalkyl, for example isopropyl, sec-butyl, tert-butyl or cyclohexyl, and R1 means C3 -C8 alkyl or the meaning methyl.

Most preferred in the compositions of the invention are compounds of the formula I4 of the formula sheet wherein R 1 is methyl, tert-butyl or cyclohexyl, especially methyl, and R 1 'is tert-butyl or cyclohexyl, especially tert-butyl , introduce. The compositions of the invention preferably contain those compounds of the formula 14 of the formula sheet, wherein n represents a number in the range 5 to 8, for example 6 to 8, in particular the number 6. Preference is also given to the compositions of the invention which further contain the alcohols of the formula 16 of the formula sheet described below,

The (O- (hydroxyphenyl) -alkanols of the formula 14 of the formula sheet can be prepared by known methods or analogously thereto, for example, the compounds of the formula 14 of the formula sheet can be prepared, for example, in accordance with US-A-4,260,832 described process or according to an analogous process thereafter, the corresponding 2,6-disubstituted phenols in the presence of alkali metal, alkali metal hydroxides or alkoxides at temperatures of from 200 to 300 ° C are removed with a ü) -alkanediol, converted. The product can then be isolated by known methods and used for the reaction with carboxylic acid derivatives of the formula V; however, it is also possible to use the crude product without further purification directly for the preparation of the compounds of the formula I.

When instead of the starting phenols described in US-A-4,260,832 a 2,6-disubstituted phenol is used, of which the substituents alkyl or cycloalkyl is none or at most one tert-butyl, the new compounds are obtained with the formula 16 of the formula sheet, in which G1 and G1 'have the meanings mentioned above for R1 and R1', but for G1 the meaning tert-butyl is excluded. As further defined above for formula 1 of the formula sheet, n represents an integer from the range of 4 to 8. A compound of the formula 16 of the formula sheet is also an object of the invention.

Preference is given to compounds of the formula 16 of the formula sheet, in which G 1 'means secondary or tertiary C 3 -C 2 Z 4 alkyl or C 5 -C 8 cycloalkyl and G 1 has the meaning C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl. Particularly preferred G1 'has the meaning of secondary or tertiary C3-C8 alkyl or C5-C8 cycloalkyl, for example ispropyl, sec-butyl, tert-butyl or cyclohexyl and G1 has the meaning C3-C8 alkyl with the exception of tert-butyl, or C5-Cg cycloalkyl or the meaning methyl. Most preferred are compounds of formula 16 of the formula sheet, wherein G 1 represents methyl or cyclohexyl, especially methyl, and G 1 'tert-butyl or cyclohexyl, especially tert-butyl.

Preference is given to those compounds of the formula 16 of the formula sheet, wherein n represents a number -in the range 5 to 8, for example 6 to 8, in particular the number 6.

Further methods, according to which, respectively, by analogy with which compounds of formula 16 of the formula sheet and the compounds of formula 14 of the formula sheet can be prepared, are for example in DE-A-2.1 ^ 7 · 5 ^ and in NL-A-79.05000 described or referenced.

As described above, the residue A in formula 1 of the formula sheet can be derived from an m-basic carboxylic acid. These may be aromatic, aliphatic, mixed aromatic-aliphatic, cycloaliphatic or bicycloaliphatic acids or their unsaturated derivatives, for example the following acids: caprylic acid, acetic acid, stearic acid, polyisobutenyl succinic acid, n-hexacosanoic acid, trimethyl acetic acid, propionic acid , isovaleric acid, lauric acid, oleic acid. acrylic acid, methacrylic acid, sorbic acid, linolenic acid, maleic acid, itaconic acid, glutaconic acid. dibasic acids, such as oxalic, amber, iso-dodecyl amber, glutaric, adipic, pimeline, cork, azelaic or sebacic acid, the polymers of fatty acids, such as the dimers and trimers thereof, such as those for example in Ind. and Eng, Chem. 33. 86-89 (19 ^ 1) have described heteroatomic acids, such as, for example, nitrilotriacetic acid, cycloaliphatic acids, such as cyclohexane carboxylic acid, 1,2- and 1,4-cyclohexadicarboxylic acid and naphthenic acids, including e.g. cyclopentane carboxylic acid, cyclopentylacetic acid, 3-methylcyclopentylacetic acid, camphoric acid, 4-methylcyclohexane carboxylic acid and 2,4,6-trimethylcyclohexane carboxylic acid, bicyclo (2,2,2) -octa-2,3-dicarboxylic acid and bicyclo- ( 2,2, 1) -hepta-5-en-2-carboxylic acid, aromatic carboxylic acids, such as benzoic acid, o-, m- and p-toluic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,4,5 -benzene tetracarboxylic acid, diphenic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalene-1,8-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,4,5-tricarboxylic acid, etc., paraffinic ω-aryl acids, such as phenylacetic acid , hydro-cinnamic acid, phenylbutyric acid, γ— (1-naphthyl) -butyric acid, ó-phenylene-n-valeric acid, € -phenyl-n-caproic acid, o-, m- or p-phenylene diacetic acid or o-phenylene acyl-β-propionic acid, as well as unsaturated phenylic acids such as, for example, cinnamic acid.

A preferred subject of the invention are compounds of the formula 17 of the formula sheet, wherein n represents an integer in the range of 4 to 8 and m represents an integer in the range of 1 to 3, A in case m = 1 ¢ ^ ¢ 35 represents alkyl which is unsubstituted or substituted by C5-C8 cycloalkyl, or represents C2-C25 alkyl which is C5-C8 cycloalkyl or one or more of the groups -S-, - 0- and / or -NR2-interrupted, or A in the case of m = 1 C5-C8 cycloalkyl, which is unsubstituted or substituted by C1-C12 alkyl or C2-C12 alkenyl, C6-C8 cycloalkenyl, which is unsubstituted or is substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl, phenyl which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl, naphthyl which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl , biphenyl, which is unsubstituted with C1-C12 alkyl or alkenyl, or C2-C25 alkenyl, C5 ~ C10 bicycloalkenyl, C7-C1 2 phenylalkyl, C 1 -C 12 phenylalkenyl, 0η-0ι8 naphthylalkyl, Cu-Cl8 naphthylalkenyl, C13-Cl8 biphenylalkyl, C13-C18 biphenylalkenyl, or a group of formula 2, represents A in case m = 2 a direct bond, C 1 -C 12 alkylene, C 2 -C 12 alkenylene, C 5 -C 8 cycloalkylene unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl, C 6 -C 8 cycloalkenylene unsubstituted or with C 1-8 C12 alkyl or C2-C12 alkenyl is substituted, C8-C10 bicycloalkenylene, phenylene, naphthylene, or C2-C1S interrupted by C1 -C8 cycloalkylene or phenylene or at least one of the groups -S-, -0- or -NR2 alkylene means, A in the case of m = 3 C 1 -C 8 alkane triyl, C 2 -C 8 olefin triyl, benzene triyl, naphthalene triyl, a trivalent group of the formula

or C 2 -C 18 alkane triyl, which is interrupted by at least one of the groups -S-, -O- or -NR 2, represents R 1 represents methyl or tert-butyl, R 2 represents H or C 1 -C 6 alkyl, R 3 and R4 independently represents C1 -C1 alkyl, and R5, R6, and R7 independently represent C1-C3alkylene.

Preferred compounds of formula 1 of the formula sheet are those in which n represents an integer in the range of 4 to 8 and m represents an integer in the range of 1 to 4; A in the case where m = 1 represents C 1 -O 25 alkyl which is unsubstituted or substituted by C 5 -C 8 cycloalkyl; or C2 -C25 represents alkyl interrupted by C5 -C8 cycloalkyl or one or more of the groups -S-, -O- and / or -NR2; or A in the case where m = 1 C 5 -C 8 cycloalkyl unsubstituted or substituted with C 1 -C 18 alkyl; C8-C8 cycloalkenyl, which is unsubstituted or substituted by C1-C12 alkyl; phenyl which is unsubstituted or substituted by C 1 -C 18 alkyl; or C2-C25alkenyl;

J.U

C 1 -C 12 phenylalkyl; or represents a group of the formula 2 of the formula sheet; A in case m = 2 a direct bond; C 1 -C 2 alkylene; C2 -C12 alkenylene; C5-C8 cycloalkylene which is unsubstituted or substituted by C1-C12 alkyl; C6 -C8 cycloalkenylene, which is unsubstituted or substituted by C1 -C12 alkyl; phenylene; a divalent heterocyclic radical from the group furan, thiophene or pyrrole which is saturated on the nitrogen atom by hydrogen or the -R 2 substituent; or A, in the case where m = 2, represents C2 -C18 alkylene interrupted by C5 -C8 cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR2; and A in the case of m = 3 C 1 -C 8 alkanetriyl; C 2 -C 8 olefin triyl; benzene triyl; a trivalent group with the formula

or C2 -C18 alkantriyl, which is interrupted by at least one of the groups -S-, -O- or -NR2; proposes; A in case m = 4 represents a benzene or cyclohexyl radical with 4 free valencies; R1 and R1 ', independently of one another, represent C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl; R2 represents H or C1 -C6 alkyl; R 3 and R 1 independently of one another are C 1 -C 6 alkyl; and R5, R6 and R7 independently represent ¢ ^ -O3 alkylene.

Compounds of formula 1 of the formula sheet, wherein R 1 'represents tert-butyl or cyclohexyl and R 1 represents methyl, tert-butyl or cyclohexyl; n is a number in the range 4 to 6; and A in the case where m = 1 represents C6 -C18 alkyl or C2 -C12 alkenyl; A in case m = 2 a direct bond; C1-C12alkylene; phenylene; the group of formula 18 of the formula sheet; or C2-C3g alkylene interrupted by 1 to 5 oxygen or sulfur atoms, A in the case where m = 3 represents a benzene triyl or a trivalent group of the formula

proposes; and A in the case where m = 4 represents a benzene residue with 4 free valencies are a particularly preferred subject.

Among those of particular significance are those compounds wherein A in the case of m = 1 C2 -C12 alkenyl; and A in the case of m = 2 phenylene; the group of formula 18 of the formula sheet; C 2 -C 36 alkylene interrupted by 1 to 5 oxygen atoms; or a group - (CH2) k represents "S- (CH2) k-, and k represents an integer in the range 1 to 3; in particular those compounds, wherein m is 1 or 2.

Also particularly preferred are those compounds of formula 1 of the formula sheet wherein n is an integer in the range from 5 to 8, especially in the range from 6 to 8, preferably 6.

Among the compounds of the formula 1 of the formula sheet, especially compounds of the formula 19 of the formula sheet stand out, wherein A is the meaning - {CH 2) j -; - (CH2) k -S- (CH2) k; group just has the formula 18 or - {CH2) 2-0- [CH2) 2-0-] j- (CH2) 2; j 0 or an integer ranging from 1 to 4; and k represent an integer ranging from 1 to 3.

Of particular significance are the following compounds a) 6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl stearate; b) 6- (3,5 "di-tert-butyl-4-hydroxyphenyl) hexyl stearate; c) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] succinate; d) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] adipate; e) bis- [6- (3 ”tert-butyl-4-hydroxy-5-methyl-phenyl) -hexy1] -suberate; f) bis- [6- (3 "tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] isophthalate; g) bis- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl] isophthalate; h) tris- [6- (3 "tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] trimellitate; j) tris- [6- (3,5 "di" tert-butyl-4-hydroxyphenyl) -hexyl] trimellitate; k) tris- [6- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -hexyl] -trimesinate; 1) tris- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl] trimesinate, as well as the compounds of formulas 21-30 of the formula sheet.

Of particular technical significance are compounds of the formula 1 of the formula sheet, wherein n is an integer ranging from 4 to 6; especially those compounds, where n is an integer in the range of 4 to 6, and where A in the case of m = 1 represents C6-C20 alkyl, A in the case of m = 2 a direct bond, (^ -0 ^ alkylene , phenylene or -S-interrupted C 2 -C 6 alkylene, and A in the case of m = 3 represents benzene triyl.

A preferred subject of the invention are further compounds of the formula 1 of the formula sheet wherein m is 2 and Δ represents /, 036 alkylene interrupted by at least one oxygen atom.

Also of interest are those compounds of the formula I of the formula sheet, wherein A in the case of m = 1 C6 -C20 alkyl, C3 -C18 alkenyl, interrupted by one or more groups -S- or -O- C1 -C. alkyl, cyclohexyl, C 1 -C 4 alkyl substituted cyclohexyl, phenyl, C 1 -C 12 alkyl substituted phenyl or phenylalkyl having a total of 7 to 9 carbon atoms, A in the case where m = 2 represents a direct bond, C 1 -C 12 alkylene, C2 -C12 alkenylene, phenylene or C2 -C3 alkyl interrupted by a group -S- or -O-, represents alkylene, and A in the case of m = 3 C1 -C8 alkane triyl, benzene triyl, alkylbenzene triyl having 7 to 10 carbon atoms or the group

proposes.

The compounds of formula I of the formula sheet are suitable for stabilizing organic materials against thermal, oxidative and actinic degradation. Particular attention should be drawn here to its excellent antioxidant activity in the stabilization of organic materials.

Examples of such materials are: 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, such as, for example, cyclopentene or norbornene ; further polyethylene (which may optionally be cross-linked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE).

Polyolefins, i.e. polymers of monoalkenes, such as those mentioned in the above paragraph, in particular polyethylene and polypropylene, can be prepared by various methods, in particular by the following methods: a) by radicals (usually under high pressure and at high temperature).

b) using a catalyst, the catalyst usually containing one or more metals of group IVb, Vb, VIb or VIII. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π- or σ-coordinated. These metal complexes can be free or fixed on a support, 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 other activating agents may be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metal elements being groups Ia, Ha and / or lilac. The activating agents can, for example, be modified with further ester, ether, amine or silyl ether groups. The catalyst systems are commonly referred to as Philips, Standard Oli Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. 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-butene-1 copolymers, propylene-isobutene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; further mixtures of such copolymers with each other and with polymers mentioned under 1).

b. v. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymer, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or statistically structured polyolefin / carbon monoxide copolymers and the blends with other polymers such as e.g. polyamides.

k. Hydrocarbon resins (e.g. C5-C9) including hydrogenated modifications thereof (e.g. tackifying resins) 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 e.g. styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, sturen-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile methacrylate; fairly high impact toughness mixture of styrene copolymers and another polymer, such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as styrene block copolymers, e.g. styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butene-styrene or styrene-ethylene / propylene-styrene.

7- Graft polymers of styrene or α-methylstyrene. such as, for example, styrene on polybutadiene, styrene on polybutadiene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styran, acrylonitrile and maleic anhydride or maleic imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates, respectively. alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene propylene diene terpolymers, styrene and acrylonitrile on polyacrylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), such as these for example as so-called ABS, MBS, ASA or AES polymers are known.

8. Halogen-containing polymers, such as, for example, polychloropene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl-fluoride. ; as well as their copolymers, 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 polyacrilonitriles.

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-alkoxy-alkyl acrylate copolymers, acrylonitrile-vinyl halide-copolymers of acrylonitrile-methyl-acrylonitrile butadiene terpolymers.

11. Polymers containing unsaturated alcohols and amines, respectively. the acyl derivatives or acetals are derived therefrom, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; as well as their copolymers with the olefins mentioned in point 1.

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

13. Polyacetals, such as polyoxymethylene, as well as 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 their mixtures with styrene polymers or polyamides.

15. Polyurethanes, those of hydroxyl-terminated polyethers, polyesters and polybutadienes, on the one hand, and aliphatic or aromatic polyisocyanates, on the other, and 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 hexamethylene diamine 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 above polyamides with polyolefins, olefin copolymers, ion lakes or chemically bonded or grafted elastomers; or with polyethers, such as, for example, 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 and polybenzimidazoles.

18. Polyesters, which are derived from dicarboxylic acids and dialcols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, polyhydroxy benzoates, and block polyether esters, which derived from hydroxyl-terminated polyethers; 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 melamine 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 and vinyl compounds as a crosslinking agent, as well as their halogen-containing, low-flammability modifications.

24. Crosslinkable acrylic resins derived from substituted acrylic esters, such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates.

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

26. Cross-linked epoxy resins derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic dipoxides.

Natural polymers, such as cellulose, natural rubber, gelatin, as well as the polymer homolog chemically derived derivatives, such as cellulose acetates, propionates and butyrates, respectively. the cellulose ethers, methyl cellulose; as well as rosin resins and derivatives thereof.

28. Blends (polyblends) of the above polymers such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBT / ABS, PC / ASA, PC / PBT, PVC / CPE ,. PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS / PPO / HIPS, PPO- / PA 6,6 and copolymers, PA / HDPE, PA / PP / PPO.

29. Natural and synthetic organic substances, which are pure monomeric compounds or mixtures thereof, for example mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates ), as well as mixtures of synthetic esters with mineral oils in arbitrary weight ratios, such as are used, for example, as spinning preparations, and their aqueous emulsions.

30. Emulsions in water of natural or synthetic rubbers, such as, for example, natural rubber latex or latices of carboxylated styrene-butadiene copolymers.

Further subjects of the invention are therefore compositions containing an organic material sensitive to oxidative, thermal and / or actinic degradation and at least one compound of the formula 1 of the formula sheet, as well as the use of the compounds of the formula 1 of the formula sheet for stabilizing organic material against oxidative, thermal or actinic degradation

The invention therefore also includes a method for stabilizing organic material against thermal, oxidative and / or actinic degradation, which is characterized in that at least one compound of the formula I of the formula sheet is added to this material.

Of particular interest is the use of compounds of the formula 1 of the formula sheet as antioxidants in synthetic organic polymers.

Preferred organic materials are polymers, for example synthetic organic polymers or mixtures of those polymers, in particular thermoplastic polymers. Particularly preferred organic materials are polyolefins and styrene copolymers, for example the materials indicated above under points 1 to 3 and 5 and 6, in particular polyethylene and polypropylene, as well as ABS and styrene-butadiene. copolymers. The preferred subject of the invention are therefore compositions in which the organic material is a synthetic organic polymer resp. is a mixture of such polymers, especially a polyolefin or a styrene copolymer.

In general, the compounds of the formula I of the formula sheet are added to the material to be stabilized in amounts of 0.01 to 10 #, preferably 0.01 to 5 #, in particular 0.01 to 2 #, based on the total weight of the material to be stabilized, added. Especially preferred is the use of the compounds according to the invention in amounts of 0.01 to 0.5 #, especially 0.05 to 0.3 # ·

In addition to the compounds of the formula I of the formula sheet, the compositions according to the invention may also contain customary additives, for example the additives indicated below.

1. Antioxidants 1.1. Alkaline monophenols. e.g. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4- m-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclo-pentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4- dimethyl-6- (1'-methyl- \ mdec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-11-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenols. e.g. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.

1.3 Hydroquinones and alkrohydroquinones. e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydrochi-non, 2,6-diphenyl-4-octadecyl -oxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -hydroxyphenyl stearate, bis- (3 * 5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Hydroxylated thiodiphenyl ethers. e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6-tert- butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3,6-di-sec-amylphenol), 4 , 4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.5. Alkylidene bisphenols. e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2'-methyl- lene-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6 -nonyl-4-methylphenol), 2,2'-methylene-bis- (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'-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylene -bis- [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-methylene-bis - (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenol) -butane, 2,6-bis- (3-tert-butyl- 5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3 "tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis- (5- tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis- [3,3 "bis- (3'-tert-butyl-4'-hydroxyphenyl) butyrate, bis- ( 3-tert-buty1-4-hydroxy-5-methy1-pheny1) -dicyclopentadiene , bis- [2- (3-tert-butyl-2'-hydroxy-5, -methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] -terephthalate, 1,1-bis- (3 .5 "dimethyl-2-hydroxyphenyl) -butane, 2,2-bis- (315-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.

1.6. 0-. N and S benzyl compounds. e.g. 3.5.3 ', 5'-Tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5 "dimethylbenzyl-mer captoacetate, tris- (3,5-di-tert-butyl-) 4-hydroxyben2yl) -amine, bis- (4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) -di-thioterephthalate, bis- (3,5-di-tert-butyl-4-hydroxy-benzyl) -sulfide t isooctyl -3.5% di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.7. Hydroxylated malonates. e.g. dioctadecyl-2,2-bis- (3.5 "di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di- dodecyl mercaptoethyl-2,2-bis- (3.5 "di-tert-butyl-4-hydroxybenzyl) -malonate, di- [4- (1,1,3,3-tetramethylbutyl) -phenyl] -2,2-bis- (3.5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.8. Hvdroxvbenzvl aromatics e.g. 1,3,5-tris- (3,5 "di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3,5-di-tert-butyl-4-hy -droxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris- (3,5 "di-tert-butyl-4-hydroxybenzyl) -phenol.

1.9. Triazine compound. e.g. 2,4-bis-octyl mercapto-6- (3,5-di-tert-butyl-4-hydroxy-anilino) -1,3.5 "triazine, 2-octyl mercapto-4,6-bis- (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3.5-2,4,6-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-bydroxy-2,6- dimethylbenzyl) isocyanaurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1.3.5 ”triazine, 1,3.5-tris- (3.5_di-tert-butyl-4 -hydroxyphenylpropionyl) -hexahydro-1,3.5-triazine, 1,3.5-tris- (3.5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.10. Benzyl phosphonates. e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of the 3,5-di-tert-butyl-4-hydroxybenzylphosphorus monoethyls ter.

1.11. Acvlaminophenols. e.g. 4-hydroxy lauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester, 1.12. Esters of β-Π.l ^ -di-teΓt-butvl-4-hvdΓoxvfenvl) -ΏΓOPl · impure with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octadecannol, 1,6-hexanediol, 1,9-nonaadiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N'-bis- (hydroxy-ethyl) -oxalic acid diamide, 3-tbiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] -octane.

1.13. Esters of fi- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octadecannol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis- (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol, trimethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane .

1.14 Esters of B- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, such as e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxy) ethyl isocyanurate, N, N'-bis - (hydroxyethyl) oxalic acid diamide, 3 "thiaundecanol, 3" thiapentadecanol, trimethyl hexanediol, trimethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicylo-clo [2.2.2] octane.

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyl-phenyllazic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxy) ethyl isocyanurate, N, N'-bis - (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol, trimethylpropane, k-hydroxymethyl-1-phospha-2,6,7-trioxabicy-col [2.2.2] octane.

1.16. Amides of B- (3,5-di-tert-butyl-4-hydroxyl-phenyl-propionic acid. Such as b, v, N, N'-bis- (3,5 "di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylene- diamine, N, N'-bis- (3.5 "di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis- (3.5 ~ di-tert-butyl-4-hydroxyphenylpropionyl) -hydra- zine.

2-UV absorbers and photoprotective agents 2.1. 2- (2 * -Hydroxyphenyl) -benztriazoles. such as e.g. 2- (2'-hydroxy-5'-methyl-phenyl) -benztriazole, 2- (31,5'-di-tert-butyl-2 * -hydroxy-phenyl) -benz-triazole, 2- (5'-tert- butyl-2'-hydroxyphenyl) -benztriazole, 2— (2'-hydroxy-5 '- (1,1,3,3 "tetramethylbutyl) phenyl) -benztriazole, 2- (3" »5'-di-tert-butyl- 2'-hydroxyphenyl) -5-chloro-benztriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methyl-phenyl) -5-chloro-benztriazole, 2- (3'-sec-butyl -5'-tert-butyl-2'-hydroxyphenyl) -benztriazole, 2- (2 '-hydroxy-4'-octoxyphenyl) -benztriazole, 2- (3' '5'-di-tert-amyl-2 1-hydroxyphenyl) -benztriazole, 2— (3 *, 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) -benztriazole, mixtures of 2- (3'-tert-butyl-2 * -) hydroxy-5 '- (2-octyloxycarbonylethyl) -phenyl) -5-chloro-benztriazole, 2- (3 * -tert-butyl-5' ~ [2- (2-ethylhexyloxy) -carbonylethyl] -2 '-hydroxyphenyl) ~ 5 ~ chlorobenztriazole, 2- (3'-ter-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzriazole, 2- (3'-tert-butyl -2 * -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -benztriazole, 2- (3'-tert-butyl-2'-hydroxy- 5 '- (2-octyloxycarbonylethyl) -phenyl) -benztriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -benztriazole, 2- (31 dead-cyl-2'-hydroxy-5'-methylphenyl) -benztriazole and 2- (3 * -tert-butyl-2'-hydroxy-5 * - (2-isooctyloxycarbinylethyl) phenyl-benztriazole, 2,2'- methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benztriazol-2-yl-phenol]; transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -benztriazole with polyethylene glycol 300; [R-CH 2 CH 2 -C00 (CH 2) 3] 2 with R '= 3'-tert-butyl-4'-hydroxy-5'-2H-benztriazol-2-yl-phenyl.

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

2.3. Esters of optionally substituted benzoic acids. such as, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis- (4-tert-butyl-benzoyl) -recorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di- tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3? 5-di-tert-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-tert-butylphenyl ester.

2.4. Acrylates. such as, for example, α-cyano-β, β-diphenylacrylic acid ethyl ester, respectively. isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or. -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (fi-carbomethoxy-fi-cyanovinyl) -2-methylindoline.

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

2.6. Sterically hindered amines. such as, for example, bis- (2,2,6,6-tetramethyl-piperidyl) sebacate, bis- (2,2,6,6-tetramethyl-piperidyl) succinate, bis- (1,2,2,6 6-pentamethylpiperidyl) sebacate, n-butyl-3 * 5-di-tert-butyl-4-hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl -2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, condensation product of N, N'-bis- (2,2,6,6-tetra-methyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5 "triazine, tris- (2,2,6,6-tetramethyl-4-piperidyl) -nitrilotri acetate, tetrakis- (2,2 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetraoate, 1,1 '- (1,2-ethanediyl) -bis- (3.3 "5" 5 "tetramethylpiperazinone) , 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-pentamethylpiperidyl) -2-n -butyl-2- (2-hydroxy-3,5-di-tert-butyl-benzyl) -malonate, 3-n-octyl-7,9,9,9-tetramethyl-1,3,8-triazospiro [4,5] decane -2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, condensation product of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino -2,6-dichloro-1,3,5-triazine, 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, condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,6,6,6-pentamethylpiperidyl) - 1,3.5 "triazine and 1,2-bis- (3-aminopropylamino) -ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazospiro [4,5] decane-2,4-dione, 3 "dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 1-iodide-cyl-1- (1,2 2,6,6-pentamethyl-4-piperidyl) -pyrrolidine-2,5-dione.

2.7. Oxalic acid diamides. such as, for example, 4,4'-di-octyloxy-oxanilide, 2,2 * -di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di -tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tart-butyl-2'-ethyl oxanilide and mixtures thereof with 2-ethoxy-2, -ethyl-5t4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy, as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxylphenyl) -1.3.5-triazines. such as, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5 "triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3.5-triazine, 2,4-bis- (2-hydroxy-4- propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) - 4.6-bis (4-methylphenyl) -1,3.5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) - 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl ] -4,6-bis (2,4-dimethylphenyl) -1,3,5 "triazine, 2- [2-hydroxy-4 - (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6 bis (2,4-dimethyl-phenyl-1,3,5-triazine.

3. Metal deactivators. such as, for example, Ν, Ν'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis- (salicyloyl) -hydrazine, N, N'-bis- (3.5 "di-tert-butyl -4-hydroxy-phenylpropionyl) -hydrazine, 3-salicyloylamino-1,2,4-triazole, bis- (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N, N'-diacetal adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide.

4. Further phosphites and phosphonites. such as, for example, triphenylphosphate, diphenylalkylphosphites, phenyldialkylphosphites, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythrit-diphosphyl, di-tert-butyl-phosphyl-phenyl-phenyl-phosphyl-phenyl-phenyl-phosphyl-phenyl-phosphetyl-phosphyl (2,4-di-tert-butylphenyl) -pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, bis-isodecyloxy pen taeritritol diphosphite, bis- (2,4-di -tert-butyl-6-methylphenyl) -pentaeritri-toldiphosphite, bis- (2,4,6-tri-tert-butylphenyl) -pentaerythritol diphosphite, tristearyl-sorbite-triphosphite, tetrakis- (2,4-di-tert-butylphenyl) ) -4,4 '-biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz [d, g] -1,3,2-dioxaphosphocin, 6- fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis- (2,4-di-tert-butyl-6- methyl phenyl) methylphosphite, bis- (2,4-di-tert-butyl-6-methylphenyl) -ethylphosphite.

5. Peroxide-destroying compounds, such as esters of JJ-thio-dipropionic acid, for example zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetra-kis (β-dodecyl mercapto) propionate.

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

7. 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 stearate, sodium ricinoleate, K palmitate, antimony pyrocation cholate or ton pyrocolate cholate.

8. Germination agents. such as, for example, 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, glimmer, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, such as e.g. plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, anti-statics, propellants.

11. Benzofuranones. resp. indolinones. such as e.g. in US-A-4,325-863 or US-A-IJ. 33 ^. 244.

The usual additives are added, for example, in concentrations from 0.01 to 102, based on the total weight of the material to be stabilized.

The incorporation of the compound of the formula (I), as well as any further additives into the organic material, takes place according to known methods. The incorporation into the materials can be, for example, by mixing or applying the compounds with the formulation

Ie 1 of the formula sheet and any further additives are carried out according to the methods customary in the art. In the case of polymers, in particular synthetic polymers, incorporation may take place before or during molding or by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the compounds of the formula I of the formula sheet into polymers consists in their addition before, during or immediately after the polymerization of the corresponding monomers or. prior to cross-linking. The compounds of the formula I of the formula sheet can be added as such, but also in encapsulated form (for example in waxes, oils or polymers). In the case of the addition before or during the polymerization, the compounds of the formula 1 of the formula sheet also acts as regulators for the chain length of the polymers (chain terminators).

The compounds of the formula (I) of the formula sheet can also be added in the form of a masterbatch, for example containing it in a concentration of 2.5 to 25% by weight, to which the materials to be stabilized are added.

The materials stabilized in this way can be used in the most diverse form, for example as films, fibers, bands, molding compositions, profiles or as binders for lacquers, adhesives or sealants.

The following examples further illustrate the invention. Partial and percentage data refer to weight, unless stated otherwise. In the formulas, the prefixes n means a straight alkyl radical, the prefixes i an isomer mixture. In the tables, "melting point" with "m.p." or "smp." abbreviated.

Example Ia: Preparation of 4- (3 "tert-butyl-5-methyl-4-hydroxyphenyl) -butanol.

50 kg of potassium hydroxide, 316 g of 2-tert-butyl-6-methylphenol and 866 g of 1,4-butanediol are placed in an autoclave. After gassing with nitrogen, the autoclave is closed and the mixture is heated to 235 * 0 (4 bar) with stirring for 6 hours; further rise in pressure due to the reaction is prevented by venting gas. After completion of the reaction, cooling to 80 ° C and emptying the autoclave. Excess butanediol is removed by distillation. The distillation residue is poured onto 1 l of water and 500 ml of toluene. The organic phase is then washed with water until neutral and the toluene is filtered off by applying vacuum. The residual residue (310 g) contains the title product of formula 31 for 68-70 #. The further purification is effected by fractional distillation under vacuum; the pure product boils at 115 ° C and 35 Pa (= 0.35 mbar). It has a refractive index n ^ ° = 1.5322.

Example Ib: preparation of 6- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -hexanol.

Example Ia is repeated with the difference that instead of 1,4-butanediol an equivalent amount of 1,6-hexanediol is used. The product obtained has the formula 32 and has a boiling point at 35 Pa (= 0.35 mbar) of 135 ° C and melts at 45 ° C.

Example Ic;

A solution of 18.9 (80 mmol) 4- (3-tert-butyl-5-methyl-4-hydroxy-phenyl) -butanol (product from Example 1a) and 9.5 S (120 mmol) pyridine in 90 ml toluene is added mixed dropwise under nitrogen with a solution of 25.5 g (84 mmol) of stearic acid chloride in 10 ml of toluene at 10 ° C. The white suspension is then allowed to warm to 20-25 ° C, filtered, the filtrate is poured onto about 1 mol HCl in water and extracted with ethyl acetate. After drying and concentrating the organic phase, the crude product obtained is purified by chromatography (SiO2; hexane: ethyl acetate = 19: 1). 37.2 g (93¾) of the product of formula 33 (compound No. 1) are obtained as a colorless liquid. Characterization (IR) and analysis can be derived from Table A.

Examples II-XVI;

For the preparation of compounds Nos. 2-16, corresponding ö) - (3-tert-butyl-5-methyl-4-hydroxyphenyl) -alkanols, respectively, are first prepared according to the method described in Example 1a. ω- (3,5 "di-tert-butyl-4-hydroxyphenyl) alkanols prepared synthetically. The starting compounds thus obtained (compounds of the formula 14 of the formula sheet) are subsequently used using corresponding acid chlorides according to the example described in Example 1c. method to the said final products (compounds of the formula I) The purity and characterization data of the compounds are presented in Tables A and B. Where no melting point is indicated, the compounds are liquid at room temperature.

Tab. A: Analysis and IR Data for Compounds No. 1-8 Compound Type: Compound of Formula 3 ^

Tab. B: Melting point, analysis and IR data of compounds No. 9 ~ 16

Connection type: compound of the formula 35

Example XVII:

In a 350 ml sulfonation flask, a colorless solution of 33 g (0.14 mol) of the product of Example Ia and 16.6 g (0.21 mol) of pyridine in 200 ml of toluene at 10 ° C under nitrogen is added dropwise mixed with 13.6 g (0.074 mol) adipic acid dichloride. The mixture is then allowed to warm to room temperature with further stirring. After 2 h, the reaction mixture is poured into hydrochloric acid in water and extracted with ethyl acetate. After drying and concentrating the organic phase, the crude product obtained is purified by chromatography (SiO2; hexane: ethyl acetate = 19: 1). 36 g (88%) of the product (compound No. 17) of the formula 36, mp 50-52 ° C, are obtained. Characterization (IR) and analysis can be derived from Table C.

Examples XVIII - XXII and XXIV - XXXIV:

For the preparation of compounds Nos. XVIII-XXII and XXIV-XXXIV, corresponding ω- (3 "tert-butyl-5" methyl-4-hydroxyphenyl) -alkanols, respectively, are first prepared according to the method described in Example 1a. (- (3,5 "di-tert-butyl-4-hydroxyphenyl) -alkanols prepared synthetically. The starting compounds thus obtained (compounds of the formula 14 of the formula sheet) are subsequently used using corresponding dicarboxylic acid dichlorides according to the example Ic method described in the said end products (compounds of formula I of the formula sheet) Data on purity and characterization of the compounds obtained are summarized in Tables C, D and E.

Example XXIII;

In a 750 ml sulfonation flask, 4.9 $ B (30 mmole) isophthalic acid, 14.4 g (70 mmole = 2.3 equivalents) of dicylohexylcarbodiimide and 150 ml of dichloromethane are mixed at 20-25 ° C under nitrogen. The resulting white suspension is dissolved in 80 ml of dichloromethane with a solution of 15.9 g (60 mmol = 2 equivalents) of 6- (3 "tert-butyl-5-methyl-4-hydroxy-phenyl) -hexanol (product from Example Ib) and a solution of 0.73 g (6 mmol) of dimethylaminopyridine in 5 ml of dichloromethane is mixed, the mixture is heated under reflux for 4 hours, then it is cooled to 20-25 ° C, filtered and evaporated. The crude product obtained (viscous oil) is chromatographically purified (SiO2; hexane / ethyl acetate = 19/1) · 11.3 B {51%) of the compound No. 23 is obtained as a colorless oil, purity and characterization data are listed in Table C.

fs ή? 1 e

Tab. C: Melting points, analysis and IR data for compounds No. 17 “23 Compound type: compound of formula 37

Tab. D: Melting points, analysis and IR data for compounds No. 24-30. Compound type: compound of formula 38

Tab. E: Analysis and IR data for compounds No. 31-34 Compound type: compound of formula 39

Example XXXV:

Example XXIII is repeated with the difference that instead of the product from example Ib, 6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexanol is started from. The product (compound No. 35) of formula 40 of the formula sheet has an IR absorption of the carbonyl bonds at 1723 cm -1.

Analysis: Ber. 77.6%, C 9.5% H, found. 77.1% C 9.53®.

Example XXXVI:

In a. round bottom flask with a distillation head, 7.57 g (30 mmole) trimellitic acid methyl ester, 33 g (117 mmole) of the product from Example 1b and 0.43 g (1.8 mmole) dibutyltin oxide were mixed. The mixture is heated to 180 ° C, where methanol is distilled off. After 2 hours, the pressure above the mixture is reduced to 533 hPa (= 400 Torr), the temperature is then kept at 180 ° C for 4 hours. Then the excess 6- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -hexanol is removed by distillation (150 ° C, 4Pa) and the crude product obtained is purified by chromatography (SiO2; first hexane, then hexane / ethyl acetate = 19/1).

24.7 g (87%) of a product of the formula 27 of the formula sheet (compound No. 36) are obtained; IR absorption of the carbonyl bands at 1722 cm1.

Analysis: Ber. 75.9% C, 8.93®, found. 75.3% C, 9.33®.

Example XXXVTT:

In a round bottom flask with distillation attachment, 16.5 g (70 mmol) of 4- (3-tert-butyl-5'-methyl-4-hydroxy-phenyl) -butanol, 18.05 (91 mmol) of 10-undecenoic acid methyl ester and 80 mg (1.4 mmol) of dibutyltin oxide.

The mixture was heated to 180 ° C, distilling methanol. After 2 hours, the pressure * above the mixture is reduced to 400 Torr and the temperature subsequently kept at 180 ° C for another 2 hours. Thereafter, the excess 10-undecenoic acid methyl ester is removed by distillation and the crude product (brown oil) obtained is chromatographically purified (SiO 2; hexane / ethyl acetate 9: 1)

23.15 g (82%) of a product of the formula 40a of the formula sheet are obtained.

Analysis and IR data: see Table F.

Example · XXXVIII - XL

Compounds XXXVIII-XL are prepared analogously to the method described in Example I. Analysis and IR data for compounds 38-40 are in Table F. The corresponding data for compounds 40 and 41 are in Table G.

Tab. F: Analysis and IT data of compounds No. 37_40; Connection type: compound of the formula 4l

Tab. G: Analysis and IR data of compounds No. 41-42 Compound type: compound of formula 42

Examples XLIII-XLV

Compound No. 43 is prepared according to the method described in Example I, Compound No. 44 is prepared according to the method described in Example XXXVII; compound No. 45 is prepared according to the method described in Example XXIII. Analysis and IR data of the compounds XLIII-XLV can be found in Table H.

Tab. H: Analysis and IR data for compounds No. 43-45. Compound type: compound of formula 43

Example XLVI: a. Esterification of the dicarboxylic acid mixture with methanol

In a solution of 52 g (0.4 mmol) dicarboxylic acid mixture (manufacturer BASF; consisting of 25-35% succinic acid, 37-47% glutaric acid and 25-30% adipic acid) in 450 ml methanol at 10 ° C, 22 ml / 0 .4 l mol of concentrated sulfuric acid is added dropwise. The resulting solution is kept under reflux temperature for 3 hours. After cooling to 20-25 ° C, the mixture is neutralized with 55 g of potassium carbonate, poured onto water and extracted with ethyl acetate. Evaporation of the solvent provides 23 g (36%) of the desired ester mixture as a pale yellow oil.

Gas chromatographic analysis of the compound mixture of the formula H3C-0C0- (CH2) x-C00-CH3: x = 2 23 mol * x = 3 44 mol # x = 4 33 mol # b) Preparation of compound 4b

In a round bottom flask with distillation design, 30.7 U (130 mmol) 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -butanol, 8.01 g (50 mmol) of the diester mixture described under (a) and 490 mg (2 mmol) of dibutyltin oxide.

The mixture is heated to 180 ° C with the distillation of methanol. The mixture was kept at 180 ° C for an additional 15 hours. After cooling to 20-25 ° C, the crude mixture is purified by chromatography (SiO2; hexane / ethyl acetate 40: 1 - ♦ 19: 1 9: 1)

17.1 g (60%) of the compound No. 46 are obtained as a yellow oil.

Analysis and IR data: see Table I.

Examples XLVII-LI

Compounds 47 and 48 were prepared using corresponding phenolic alcohols by the method described in Example XLVI.

For the preparation of the compounds 49, 50 and 51, the corresponding methyl ester is synthetically prepared from poly-THF-dipropionic acid® 350 (manufacturer: Bayer A.G., Leverkusen) according to the method described in example XLVI. The high molecular weight dicarboxylic acid methyl ester thus obtained is subsequently converted into the said end products using corresponding phenolic alcohols according to the method described in Example XLVI.

Analysis and IR data of compounds 46-51 can be found in Table I.

Table I: Analysis and IR data for the compound 46-51 Compound type: (diester mixtures and oligomers)

Compound of formula 44

Me = methyl; t-bu = tert.butyl * Analysis calculated for x = 3

Example Lil: a) Preparation of the nitrilo-triazine acid methyl ester

To a suspension of 100 g (0.52 mol) of nitrilotriacetic acid in 200 ml of methanol, at about 10 ° C, 74.8 ml (137.7 g) of 1.4 mol) of concentrated sulfuric acid are added dropwise.

The mixture is kept under reflux temperature for 22 hours. After cooling to room temperature, the mixture is neutralized by carefully adding 15 g of potassium carbonate, poured onto water and extracted with ethyl acetate.

Evaporation of the solvent and drying the residue under vacuum provide 57 S (47 $) nitrilotriacetic acid methyl ester as a colorless oil.

IR (film on KBr crystal): carbonyl absorption at 1751 cm -1

Analysis: Ber. 46.35 /. C, 6.48 /. H, 6.0 /. N

found. 46.47 / C, 6.53 / H, 6.14 / N

b) Preparation of compound 52

In a round bottom flask with distillation design, 1.76 g (7.5 mmol) of nitrilo-triacetic acid methyl ester, 7 g (29.4 mmol) of 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) - butanol and 25 mg (0.45 mmol) of dibutyltin oxide. The mixture is heated to 180 ° C, distilling methanol. After 3 hours, the pressure is lowered to 400 Torr, and the mixture is kept at 180 ° C for an additional 2 hours.

Then, the excess 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -butanol was removed by distillation (150 ° C / 0.4 Pa) and the crude product obtained was purified by chromatography (SiO 2; hexane-ethyl acetate 9: 1 - ♦ 3: 1).

5.6 g (88%) of a product of the formula 45- are obtained

Analysis and IR data: see Table J.

Examples LIII-LV:

The compounds 53 "55 are prepared according to the method described in Example Lil. Analysis and IR data of the compounds are summarized in Table J.

Table J: Connection type: compound of the formula 46

Example LVI-LX:

The compound 56-60 is prepared according to the method described in Example XXXVI. Analysis and IR data of the compounds are summarized in Table K.

Table K: Connection type: compound of the formula 49

Example LXI;

Preparation of 4- Π.b-dicvclohexvl-4-hvdroxvfenvl) -hexanol

In a sulfonation flask, 258 g (1 mol) of 2,6-dicyclohexylphenol, 591 g (5 mol) of 1,6-hexanediol are melted and heated with g (0.64 mol) of potassium hydroxide at 238 ° C for 10 hours. The mixture is then made slightly acidic at 80 ° C with a two-molar solution of HCl in water. The phases are separated, the inorganic phase is washed with toluene and the combined organic phases are concentrated on a rotary evaporator. Excess 1,6-hexanediol and unreacted 2,6-dicylohexylphenol are removed by distillation.

Crystallization of the residue with gasoline at boiling limits 80-110 ° C yields 163 g (45 $) of a product of formula 48.

Mp .: 96 ° C

Analysis: Ber. 80.39% C, 10.68¾H

found. 78.62¾ C, 10.62¾ H

Example LXII: 32.3 g (90 mmol) of 4- (3,5 "dicyclohexyl-4-hydroxyphenyl) -hexanol using 9.2 g (50 mmol) of adipic acid dichloride according to the method described in Example 1c to 47 #) of a product of formula 49. The compound is obtained as a viscous oil.

IR (film on KBr crystal): 1736.1717 cm'1 (C = 0)

Analysis; ber. 77i76 # C, 10.29 # H found. 77.62 # C, 10.05 # H

Application examples

Example LXIII; Stabilization of nolypropylene 100 parts of polypropylene powder containing 0.1 # calcium stearate are mixed with 0.3 # distearyl thiodipropionate (DSTDP) and 0.1 # of the stabilizer of the invention shown in Table L and then in a Brabender plastograph at 200 ° Kneaded for 10 minutes.

The mass thus obtained was pressed in a press with a surface temperature of 260 ° C into plates with a thickness of 1 mm, from which strips with a width of 1 cm and a length of 10 cm were punched. For comparison purposes, a further sample without stabilizers is prepared. Several such strips were hung from each plate in a circulating air oven heated to 135 ° C or 149 ° C and observed after regular time periods. The oxidative decomposition of these strips can be seen through a yellow discoloration starting as a kind of circle. A measure of the stability of the sample is the time in days to decomposition.

Table L; Time (in days) to decomposition of the samples, containing the stabilizer combination 0.3% DSTDP + 0.1% compound of the invention, respectively. no stabilizer

Stabilizers Number of days in the oven from aging to decomposition

at 135 ° C at 149 ° C

none 1 <1 - DSTDP + Verb.Nr. 8 126 50 DSTDP + Verb.Nr. 13 i15 40 DSTDP + Verb. No. 17 155 65 DSTDP + Verb. No. 20 162 60 DSTDP + Verb. No. 21 175 33 DSTDP + Verb. No. 22 247 57 DSTDP + Ve ^ b. No. 23 -245- “85” DSTDP + Verb. No. 24. 140 43 DSTDP + Verb. No. 25 121 24 DSTDP + Verb. N & 26 151 33 DSTDP + Verb. No. 28 147 47 DSTDP + Verb. No. 29 145 49 DSTDP + Verb No. 30 194 50 DSTDP + Verb No. 35 148 50 DSTDP + Verb No. 36 190 71 DSTDP + \ erb No. 52.15g 55 DSTDP + Verb No. 53 158 · 48 DSTDP + Verb No. 54 161 55 DSTDP + Verb No. 55 150 43 DSTDP + Verb No. 56 170 52 DSTDP + Verb No. 57 193 7q DSTDP + Verb No. 58 173 52 DSTDP + Verb No. 59 163 63 "DSJDP + Verb. No. 60 159" 4g

Example LXIII: Stabilization of Aclonflonitrile-Butadiene-Stentreter Polymer (ABS) _

The stabilizers listed in Table M are dissolved in 40 ml of a mixture of hexane and isopropanol. The solution is brought to a dispersion of 100 g of ABS in 600 ml of water with vigorous stirring, after which the solution is completely absorbed by the ABS for approximately 1 minute. The polymer powder containing the stabilizers is then filtered off and dried in vacuo at 40 ° C for 40 hours.

The further processing steps are also carried out with a sample without stabilizers for comparison purposes.

2% titanium dioxide and 1% ethylene bis-stearic acid amide as a lubricant are added to the dry powder. The mixture is then compounded on a two-roll chair at 180 ° C over 4 minutes.

A sheet with a thickness of 0.8 mm is pressed from the roll sheet at 175 ° C, from which test pieces of 45 x 17 mm are punched out. The effectiveness of the added stabilizers is tested by aging in heat in a circulating air oven at 180 ° C. The color development after a 45-minute trial period serves as the criterion. The color intensity is determined according to ASTM D I925-7O (Yel-lowness Index). The test results are summarized in Table M. Higher numbers mean a more intensive yellowing. The tests show that the yellow coloration is effectively suppressed by the compound according to the invention.

Table M Yellowness Index after 45 min. Aging in the oven of samples containing no stabilizers, 0.3% dilauryl thiodipropionate (DLTDP), as well as 0.3% DLTDP + 0.23% of the indicated compound of the invention

Stabilizers Yellowness Index after 45 minutes at 180 ° C

none 78 DLTDP 75 DLTDP + Verb. No. 1 26 DLTDP + Verb.Nr. 7 25 'DLTDP + Verb.Nr. 8 26 DLTDP + Verb. No. 12 34 DLTDP + Verb.Nr. 13 39 DLTDP + Verb.Nr. 15 33 DLTDP + Verb. 16 34 DLTDP + Verb. No. 17 26 DLTDP + Verb. No. 19 31 DLTDP + Verb. No. 20 26 DLTDP + Verb. No. 21 33 DLTDP + Verb. No. 22 _ 21 DLTDP + Verb. No. 23 29 DLTDP + Verb. No. 24 32 DLTDP + Verb. No. 25 "" 41 DLTDP + Verb. No. 26 28 DLTDP + Verb. No. 28 30 DLTDP + Verb. No. 29 32 DLTDP + Verb. No. 31. 29 DLTDP + Verb. No. 32 27 DLTDP + Verb. 33 32 DLTDP + Verb No. 34 30 DLTDP + Verb No. 39 36 DLTDP + Verb No. 40 26 DLTDP + Verb No. 42 32

Example LXIV

Stabilization of X-SBR latex (carboxylated SBR latex)

Each time 0.25 parts by weight of the compounds of the invention shown in Table N are dissolved in little methanol and taken up in 100 parts by weight of X-SBR latex (styrene-butadiene copolymer) by stirring. Subsequently, a precisely defined amount of latex is filled into petri dishes and dried in a drying cabinet at 80 ° C. Transparent films with a layer thickness of about 0.2 mm are obtained. A sample without stabilizers is prepared for comparison purposes.

The effectiveness of the added stabilizers is tested by aging in heat in a circulating air oven at a temperature of 135 ° C. The discoloration of the samples is determined according to ASTM D 1925-70 {Yellowness Index) according to the time periods shown in Table N. The test data are shown in Table N. Higher numbers mean a more intensive yellow coloring. The tests show that the yellow coloring is effectively suppressed by the compounds according to the invention.

Table N: Yellowness Index after the indicated aging time at 135 ° C

Yellowness Index after aging (in hours) Stabilizer 4 12 24 40 none 92 * * * 0.25 # Comp. 31 46 52 64 75 0.25% Comp. 32 40 46 58 69 *: not measurable (sample black)

Claims (22)

1. Hangings of the formula 1, characterized by the formula 1 of the formula sheet wherein n represents an integer in the range from 4 to 8 and m represents an integer in the range from 1 to 4; A in the case where m = 1 represents C 1 -C 25 alkyl which is unsubstituted or substituted by C 5 -C 8 cycloalkyl; or C 2 -C 25 alkyl interrupted by C 5 -C 8 cycloalkyl or one or more of the groups -S-, -O- and / or -NR 2; or A in the case where m = 1 C5 -C8 cycloalkyl, which is unsubstituted or substituted by C1 -C12 alkyl or C2 -C12 alkenyl; C6-C8 cycloalkenyl, which is unsubstituted or substituted by C1-C12 alkyl or C2-C {2 alkenyl; phenyl, which is unsubstituted or substituted by -012 ^ alkyl or C 2 -C 12 alkenyl radical; naphthyl, which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2-12 alkenyl; biphenyl, which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; or C2-C25alkenyl; C6-C10 bicycloalkenyl; C7C12 phenylalkyl; C8-C12 phenylakenyl; Cu-Cl6 naphthylalkyl; C12 -C16 naphthylalkenyl; C13 -C18 biphenylalkyl; C 1 -C 2 biphenylalkenyl; or represents a group of the formula 2 of the formula sheet; A in case m = 2 a direct bond; C 1 -C 4 alkylene; C2-C12alkenylene; C5-C8 cycloalkene, which is unsubstituted or substituted by C1-C12 alkyl or C2-C12 alkenyl; C8-C8 cycloalkenylene, which is unsubstituted or substituted with C1-C12 alkyl or C2-C12 alkenyl; C8-C10 bicycloalkenylene; phenylene; naphthylene; a divalent heterocyclic radical from the group furan, thiophene or pyrrole, which is saturated on the nitrogen atom by hydrogen or the -R 2 substituent; or A, in the case where m = 2, represents C 5 -C 8 cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR 2 interrupted C 2 -C 38 alkylene; A in the case where m = 3 C 1 -C 8 alkanetriyl; C2 -C8 olefin triyl; benzenetriyl; naphthalene triyl; a trivalent group with the formula

or C 2 -C 18 represents alkanetriyl interrupted by at least one of the groups -S-, -O- or -NR 2; A in the case where m = 4 is a benzene; represents naphthyl, tetrahydrofuryl or cyclohexyl radical with 4 free valencies; R1 and R1 'independently represent alkyl or C5 -C8 cycloalkyl; R2 represents H or C1 -C6 alkyl; R3 and R4 independently of one another (Ι, -Οή alkyl; and R5, R6 and R7 independently of each other represent alkylene. A compound of the formula 1 according to claim 1, characterized in that R 1 'means secondary or tertiary C 3 -C 2 alkyl, or C 5 -C 8 cycloalkyl; and R 1 has the meaning of C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl. A compound of the formula 1 according to claim 1, characterized in that R 1 has the meaning ter-butyl and R 1 has the meaning methyl. A compound of the formula la, characterized by the formula 17 of the formula sheet wherein n represents an integer in the range from 4 to 8 and m represents an integer in the range from 1 to 3; A in the case where m = 1 represents C 1 -C 18 alkyl which is unsubstituted or is substituted by C 5 -C 8 cycloalkyl; or C2 -C25 alkyl interrupted by C8 -C8 cycloalkyl or one or more of the groups -S-, -O- and / or -NR2; or A in the case of m = 1 C 5 -C 6 cycloalkyl which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C6-C8 cycloalkenyl, which is unsubstituted or substituted with Cx-C12 alkyl or C2-C12 alkenyl; phenyl, which is unsubstituted or substituted with p1-12 alkyl or C 2 -C 12 alkenyl; naphthyl, which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; biphenyl, which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl, or C 2 -C 25 alkenyl; Cg-C10 bicycloalkenyl; C 1 -C 12 phenylalkyl; C 1 -C 12 phenylalkenyl; C12 -C18 naphthylalkyl; C11 -C1 (; naphthylalkenyl; C13 -C18 biphenylalkyl; C13 -C18 biphenylalkenyl; or a group of formula 2 of the formula sheet; A in case m = 2 represents a direct bond; C1-C12alkylene, C2-C12 alkenylene; C5 -C8 cycloalkylene, which is unsubstituted or substituted with 0Χ-012 alkyl or C2-C12 alkenyl, C6 -Cg cycloalkenylene, which is unsubstituted or substituted by C1 -C18 alkyl or C2 -C12 alkenyl; C10 represents bicycloalkenylene, phenylene, naphthylene or C5 -C8 cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR2-interrupted C2 -C18 alkylene; A in case m = 3 C ^ -Cg alkane triyl; C 2 -C 6 alkene triyl, naphthalene triyl; a trivalent group of the formula

or C 2 -C 18 alkanetriyl interrupted by at least one of the groups -S-, -O- or -NR 2; proposes; R1 represents methyl or tert-butyl; R2 represents H or C1 -C18 alkyl; R3 and R * independently represent C 1 -C 3 alkyl, and R 5, R 6 and R 7 independently represent C 1 -C 3 alkylene. A compound of the formula 1 of the formula sheet according to claim 1, wherein a in the case of m * 1 represents C 1 -C 8 alkyl, which is unsubstituted or substituted by C 5 -C 8 cycloalkyl; or C 2 -C 25 alkyl interrupted by C 5 -C 8 cycloalkyl or one or more of the groups -S-, -O- and / or -NR2; or A in the case where m = 1 C5 -C8 cycloalkyl which is unsubstituted or substituted by C1 -C12 alkyl; C8-C8 cycloalkenyl, which is unsubstituted or substituted by C1-C12 alkyl; phenyl which is unsubstituted or substituted by C 1 -C 12 alkyl; or C2-C25alkenyl; C7-C12 phenylalkyl; or represents a group of the formula 2 of the formula sheet; A in case m = 2 a direct bond; C1-C12alkylene, C2-C12alkenylene; C5-C8 cycloalkylene, which is unsubstituted or substituted by C1-C12 alkyl or C2-C12 alkenyl, C6-C8 cycloalkenylene, which is unsubstituted or substituted by C 1 -C 2 alkyl or C 2 -C 2 alkenyl; ^ 6 "^ ιο represents bicycloalkenylene, phenylene, naphthylene or C5-C8 cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR2-interrupted C2 -C18 alkylene; A in case m = 3 (^ - (¼ alkane triyl; C2-C8 olefin triyl, naphthalene triyl; a trivalent group of the formula

or C2 -C18 alkantriyl, which is interrupted by at least one of the groups -S-, -O- or -NR2; proposes; A in case m = 4 represents a benzene or cyclohexyl radical with 4 free valance requirement. A compound of the formula 1 of the formula sheet according to claim 1, characterized in that R 1 'represents tert-butyl or cyclohexyl and R 1 represents methyl, tert-butyl or cyclohexyl; n is a number from the range of 4 to 6; and A in the case where m = 1 represents C8 -C18 alkyl or C2 -C12 alkenyl; A in the case of m = 2 a direct bond, C 1 -C 12 alkylene; phenylene; the. group of the formula 18 of the formula sheet; or C2 -C36 alkylene interrupted by 1 to 5 oxygen or sulfur atoms; A in the case of m = 3 benzenetriyl or a trivalent group of the formula

proposes; and A in case m = 4 represents a benzene residue with 4 free valencies. A compound of the formula 1 of the formula sheet according to claim 1, characterized in that n is an integer in the range from 5 to 8. A compound of the formula 1 of the formula sheet according to claim 1, characterized in that n is an integer in the range from 6 to 8. A compound of the formula 1 according to claim 6, wherein m is 1 or 2. A compound of the formula 1 according to claim 9 * of the formula 50 of the formula sheet wherein A is the meaning - (CH 2) j -; - (CH2) k -S- (CH2) k; a group of the formula 18 or - (CH2) 2-0 - [(CH2) 2-0 -], - (CH2) 2; j 0 or an integer ranging from 1 to 4 and k representing a number ranging from 1 to 3. 11. One of the compounds (a) to (1) a) 6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl stearate; b) 6- (3.5 "di-tert-butyl-4-hydroxyphenyl) -hexyl stearate; c) bis- [6- (3" tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] succinate; d) bis- [6- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -hexyl] -adipate; e) bis- [6- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -hexyl] -suberate; f) bis- [6- (3 "tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] isophthalate; g) bis- [6- (3,5 "di-tert-butyl-4-hydroxyphenyl) -hexyl] isophthalate; h) tris- [6- (3- tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] trimellitate; j) tris- [6- (3.5 "di-tert-butyl-4-hydroxyphenyl) -hexyl] trimellitate; k) tris- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] trimesinate; or l) tris- [6- (3,5 "di-tert-butyl-4-hydroxyphenyl) -hexyl] trimesinate according to claim 1. 12. Compounds of formula 16 of the formula sheet, wherein G1 and G1 ', independently of one another, represent C 1 -C 18 alkyl or C 5 -C 8 cycloalkyl, excluding for G1 the meaning tert-butyl, and n an integer in represents the range from 4 to 8. Compound according to claim 12, characterized in that G1 'represents tert-butyl or cyclohexyl and G1 represents methyl or cyclohexyl. A composition comprising an organic material sensitive to thermal, oxidative and / or actinic degradation and at least one compound of the formula 1 according to claim 1. The composition of claim 14, wherein the organic material is a synthetic organic polymer or a mixture of such polymers. The composition of claim 15 wherein the synthetic organic polymer is a polyolefin or a styrene copolymer. Use of compounds of the formula 1 according to claim 1 for stabilizing organic material against thermal, oxidative and / or actinic degradation. Use according to claim 17 of compounds of the formula 1 of the formula sheet as antioxidants in synthetic organic polymers. Method for stabilizing organic material against thermal, oxidative and / or actinic degradation, characterized in that at least one compound of the formula 1 according to claim 1 is added to this material. A composition comprising an organic material sensitive to thermal, oxidative and / or actinic degradation and at least one compound of the formula 14 of the formula sheet, wherein the n is an integer in the range of 4 to 8 and R1 and R1 ' independently represent C 1 -C 18 alkyl or C 5 -C 8 cycloalkyl. Use of the compounds of the formula I according to claim 20 for stabilizing organic matter against thermal, oxidative and / or actinic degradation. Shaped article, consisting wholly or in part of a composition according to one or more of claims 14 to 21.