FR2687667A1 - CARBOXYLIC ACID ESTERS OF HYDROXYPHENYLALCANOLS AS STABILIZERS. - Google Patents

Abstract

New compounds corresponding to formula I: (CF DRAWING IN BOPI) in which n denotes an integer between 4 and 8 and m an integer between 1 and 4; A represents the aliphatic, aromatic, araliphatic or heterocyclic radical of a mono- to tetravalent carboxylic acid; and R1 and R1 'independently of each other represent a C1 -C10 alkyl or C1 -C8 cycloalkyl group. They are suitable for the stabilization of an organic material with respect to thermal, oxidative or actinic degradation.

Description

Esters of carboxylic acids of hydroxyphenylalkanols

as stabilizers.

  The present invention relates to novel esters

  of carboxylic acids of co (3,5-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 o- (3,5-dialkyl-4-

  hydroxyphenyl) -alkanols. The use of esters of co-hydroxyphenyl-c-carboxylic acid esters as stabilizers for

  organic matter is known.

  A series of publications deals with corresponding inverse esters: GB-A-1 504 573, DE-A-2 147 544,

  EP-B-171 139, EP-A-349 380, NL-A-79-05000, GB-A-

  1,509,876, Chem Abstr 84 106614c, Chem Abstr 106

  156001 u, US-A-4,910,286, US-A-4,311,637, US-A-

  4,104,252 and US-A-3,919,097 disclose esters

  of carboxylic acids of 3- (3,5-di-tert-butyl-4-

  hydroxyphenyl) -alkan-1-ol, 3- (3-tert-butyl-5-methyl-4-

  hydroxyphenyl) -alkan-1-ol and various 4- (3,5-dialkyl-4-

  hydroxyphenyl) -alcan-1-ol and their use

as stabilizers of the polymers.

  Some acid esters have now been found

  carboxylic acids of o (3,5-dialkyl-4-hydroxyphenyl) -

  alkanols with stabilizing properties

particularly good.

  One of the objectives of the present invention is thus compounds corresponding to formula I:

-30 OH

I

R R 1 '

(CH 2) C A ()

  wherein N is an integer from 4 to 8 and m is an integer from 1 to 4; A, in the case where m is 1, represents a C 1 -C 2 alkyl group which is unsubstituted or substituted or by a C 1 -C 8 cycloalkyl group; or it represents a C 2 -C 25 alkyl group which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of the groups -S-, -O and / or -NR 2; or in the case where m is 1, A is C 5 -C 8 cycloalkyl which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C 6 -C 8 cycloalkenyl which is unsubstituted or substituted by 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 by 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 a C 2 -C 25 alkenyl group; C 6 -C 20 bicycloalkenyl; C 7 -C 12 phenylalkyl; C 8 -C 12 phenylalkenyl; C1-C16 naphthylalkyl; C 12 -C 16 naphthylalkenyl; C 13 -C 18 biphenylalkyl; C14-C18 biphenylalkenyl; or a group of formula II: R 4

-CH 2 CH 2 OH (I)

R 3

  in the case where m is 2, A denotes a direct bond; a C 1 -C 12 alkylene group; C 2 -C 12 alkenylene; C 1 -C 8 cycloalkylene which is unsubstituted or substituted with C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C 6 -C 8 cycloalkenylene which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C 6 -C 10 bicycloalkenylene; phenylene; naphthylene; a divalent heterocyclic radical selected from furan, thiophene or pyrrole, which is saturated on the nitrogen atom with hydrogen atoms or the substituent -R 2; or else A, in the case where om is 2, denotes a C 2 -C 36 alkylene group interrupted by a C 5 -C 8 cycloalkylene or phenylene group or by at least one of the groups -S-, -O or -NR 2; A, in the case where m is 3, denotes a C 1 -C 8 alkanetriyl group; C 2 -C 8 alkenenediyl; benzotriyle; naphtalènetriyle; a trivalent RG-group corresponding to the formula -R 5 -N-R 7 or a C 2 -C 18 alkanetriyl group which is interrupted by at least one of -S-, -O or -NR 2 groups; A, in the case where m is 4, denotes a benzene radical; naphthyl; tetrahydrofuryl or cyclohexyl having 4 free valencies; R 1 and R 1 'independently of one another are C 1 -C 24 alkyl or C 5 -C 8 cycloalkyl; R 2 represents an H atom or a C 1 -C 4 alkyl group; R 3 and R 4 denote independently of one another a C 1 -C 4 alkyl group; and R 5, R 6 and R 7 independently of one another represent an alkylene group

Cl-C 3.

  When they represent a C 1 -C 24 alkyl or C 5 -C 8 cycloalkyl group, R 1 and R 1 'denote, independently of one another, for example a methyl, ethyl, propyl, butyl or pentyl group. , hexyl, heptyl, octyl, nonyl, decyl, cyclopentenyl, cyclohexyl, cycloheptyl or cyclooctyl. R 1 'is preferably a secondary or tertiary C 3 -C 24 alkyl group, for example a 2-butyl (sec-butyl), tert-butyl, 2-pentyl, 2-hexyl or 3-hexyl group, or R 1 'is a C 5 -C 8 cycloalkyl group, for example a cyclohexyl group, and R 1 a C 1 -C 10 alkyl group;

or C 5 -C 8 cycloalkyl.

  It is particularly preferred that R 1 'denotes a secondary or tertiary C 3 -C 18 alkyl group or a C 5 -C 8 cycloalkyl group, for example an isopropyl, sec-butyl, tert-butyl or cyclohexyl group, and R 1 an alkyl group. C 3 -C 8 or a C 5 -C 8 cycloalkyl or a methyl group Compounds of formula I in which R 1 denotes a methyl, tert-butyl or cyclohexyl group, in particular a methyl group, are particularly preferred. , and that R 1 'denotes a tert-butyl group

  or cyclohexyl, in particular a tert-butyl group.

  R 2, R 3 and R 4, when they denote a C 1 -C 4 alkyl group, represent a methyl, ethyl, 1-propyl (n-propyl), 2-propyl (isopropyl) or 1-butyl group ( n-butyl),

  2-butyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1-

  dimethylethyl (tert-butyl), a methyl group is preferred

or tert-butyl.

  When they are a C 1 -C 3 alkylene group, R 5, R 6 and R 7 denote a methylene, 1,1 or 1,2-ethylene or 1,1-, 1,2-, 2,2-group. or 1,3-propylene A methylene group is preferred. If A represents a C 1 -C 25 alkyl group, it is a branched or unbranched radical, for example a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or isobutyl radical, tert-butyl, 2-ethylbutyl,

  n-pentyl, isopentyl, 1-methylpentyl, 1,3-di-

  methylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,

  isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-

  methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-

  trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,

  decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-

  hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl or pentacosyl; an unbranched alkyl group is preferred, and

  more preferably an unbranched C 6 -C 18 alkyl group.

  A, when it denotes a C 1 -C 25 alkyl group substituted with a C 5 -C 8 cycloalkyl group, is for example a cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl or cyclohexylethyl group,

  2-cyclohexyl-n-propyl, 3-cyclohexyl-n-propyl, 4-cyclopropyl

  hexyl-n-butyl. A, when it denotes a C 2 -C 25 alkyl group interrupted by a C 5 -C 8 cycloalkyl group or by one or more of the groups -S-, -O and / or -NR 2, represents one of alkyl radicals described above with the exception of the methyl radical, in the chain of which a cyclopentylene or pentylidene, cyclohexylene or hexylidene, cyclooctylene or heptylidene, cyclooctylene or octylidene group has been introduced at one place, or in one or more places the groups mentioned above with heteroatoms A therefore responds for example to the formulas

  -C 6 H 12 3, -CH 2 -CH 4 H 9, -C 2 H 4 -O-C 2 H 4 -O-C 12 H 25, -C 18 H 36 -N (C 4 H 9) 2 AT

  A, when it is a C 5 -C 8 cycloalkyl or C 6 -C 8 cycloalkenyl which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl, may for example be a cyclopentyl group,

  cyclohexyl, cycloheptyl, cyclooctyl, 1 or 4

  cyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, 2-cyclohexenyl, 3-cycloheptenyl, cyclooctatetraenyl, 4-tert-butyl-cyclohex-2-enyl. Cyclohexyl and cyclohexenyl are preferred,

especially the cyclohexyl group.

  A, when it denotes a phenyl, naphthyl or biphenyl group substituted by a C 1 -C 2 alkyl or C 2 -C 12 alkenyl group, designates, inter alia, a methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, vinylphenyl or diethylphenyl group, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, methyl-di-t-butylphenyl, 1,1,3,3-tetramethylbutylphenyl 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.

  Here, a phenyl group is substituted, which is optionally substituted with one to three, for example one to two, in particular a C 1 -C 4 alkyl group, mainly a

methyl group.

  When it denotes a C 2 -C 25 alkenyl group, A is for example a vinyl, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl or n-penta-2,4-dienyl group,

  3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-

  dodecenyl-n-octadec-2-enyl, n-octadec-4-enyl.

  When it denotes a C 7 -C 12 phenylalkyl group, a C 7 -C 12 phenylalkenyl group, a C 1 -C 16 naphthylalkyl group, a C 1 -C 16 naphthylalkenyl group or a C 13 -C 14 biphenylalkyl group. 8 or a C 13 -C 18 biphenylalkenyl group, A represents a C 1 -C 6 alkyl or C 1 -C 6 alkenyl group which is substituted by a phenyl, naphthyl or biphenyl group such as benzyl, phenethyl, 3 phenylpropyl,? -methylbenzyl,?,? - 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-biphenylyl) -pent-3-en-1-

yl.

  When denotes a C 6 -C 20 bicycloalkenyl or C 6 -C 10 bicycloalkenylene group, A is a monovalent or divalent C 6 -C 10 bicyclic unsaturated radical which, when a monovalent radical is present, is for example, a bicyclo (2,2,1) -hepta-5-en-2-yl group, and when it is a divalent radical, may for example be in the formulas II IL or The divalent radicals (for m = 2) , trivalents (for m = 3) and tetravalents (for m = 4) derive from the monovalent radicals mentioned above A divalent radical is distinguished from the corresponding monovalent radical in that it contains instead of a hydrogen atom, an open connection; a trivalent radical is distinguished from the corresponding monovalent radical in that it contains instead of two hydrogen atoms, two open bonds; a tetravalent radical is distinguished from the corresponding monovalent radical in that it contains, instead of three hydrogen atoms, three open bonds. Thus, A, within the meaning of the indicated meanings, may, for example, be a divalent radical, also represent a radical methylene, ethylene, -CH 2 -C (CH 3) 2 -CH 2, prop-2-en-ylidene, propylene- (1,3), butylene- (1,4) , pentylene- (1,5), hexylene- (1,6), o-, m- or p-phenylene, -CH 2 / H 2-, CH 2 'CH 2 H 2 CH 2 C 2 H 4-SC 2 H 4 or -C 2 H 4 -OC 2 H 4, S 'it represents a trivalent radical, it will be for example CH 2 I, C 27 or, sf il -CH 2-CH-CH 2-, -CH 2 CH 2 'i

  represents a tetravalent radical, it will be for example -

  The novel esters of formula I can be prepared by esterification or

  transesterification common from 0-hydroxyphenyl-

  alkanols having the formula IV OH

'R 1

I 9 (IV)

(CH 2) OH

  and organic carboxylic acids having formula V

HO-C A '(V)

  or derivatives of these carboxylic acids, for example by the methods described in Tetrahedron 36, 2409 (1980) The symbols R1, RT ', A, N and m of formulas IV and V have the meanings given above for formula I Suitable carboxylic acid derivatives are, for example, anhydrides, chlorides or lower alkyl esters, for example methyl or ethyl esters. In these syntheses, appropriate esterification catalysts such as mineral acids may be used where appropriate ( for example sulfuric acid)

  or sulphonic acids (for example p-toluene

  sulfonic acid). The reaction can be carried out in a manner known per se, advantageously by addition of one of the two starting substances to the second starting substance and mixing of the two reaction partners, preferably in the absence of oxygen. be carried out in the presence of a solvent, for example toluene, or without solvent The temperature is not critical, it may be between the melting point and the boiling point of the reaction mixture, for example between and 100 C, preferably between 0 and 50 OC. 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. extraction as well as for the chromatographic purification step, hexane, ethyl acetate

or their mixtures.

  If the acid chloride is used in the reaction as a derivative of the carboxylic acid of formula V, an acid acceptor such as amines such as pyridine or triethylamine is advantageously added to the reaction mixture. It is preferred that 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 from 1.2 to 1.7 equivalents per

compared to the acid chloride.

  If the reaction is carried out in the form of a transesterification of an alcohol of formula IV with the ester of a carboxylic acid of formula V, the reaction mixture is advantageously added to the reaction mixture with ordinary transesterification catalysts. are for example organic or inorganic bases (for example lithium amide, lithium methoxide, potassium hydroxide, etc.) or Lewis acids (for example dibutyl tin oxide). If the carboxylic acid of formula V and the alcohol of formula IV are used directly as starting materials, the reaction is advantageously carried out using a water separator, distilling off the water and / or using reagents that fix the released water, such as

  for example dicyclohexylcarbodiimide.

  The use of carboxylic acid mixtures of formula V or their derivatives may be of particular practical interest for the preparation of the compounds of formula I These mixtures may be used for the synthesis as described above, and corresponding mixtures of compounds of formula I are obtained. Mixtures of compounds having formula I may be

  used as such as stabilizers.

  The alcohols corresponding to formula IV are already active by themselves as stabilizers. Compositions containing a) an organic material sensitive to oxidative, thermal and / or actinic degradation and b) a compound corresponding to formula IV, as well as The use of compounds of formula IV for the stabilization of an organic material against oxidative, thermal or actinic degradation constitutes

  therefore other objects of the invention.

  The compositions according to the invention preferably contain compounds corresponding to formula IV in which R 1 'denotes a secondary or tertiary C 3 -C 24 alkyl group or C 5 -C 8 cycloalkyl group; and R 'denotes a C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl group. It is particularly preferred that R "' denotes a C 3 -C 18 secondary or tertiary alkyl or C 5 -C 8 cycloalkyl group, Examples are isopropyl, sec-butyl, tert-butyl or cyclohexyl, and R 1 is C 3 -C 8 alkyl, C 5 -C 8 cycloalkyl or methyl, and is most preferred in the compositions according to the present invention. compounds according to formula IV wherein R 1 is methyl, tert-butyl or cyclohexyl, in particular methyl, and R 1 'is tert-butyl or cyclohexyl,

particularly tert-butyl.

  The compositions according to the invention preferably contain compounds of formula IV in which N represents a number between 5 and 8,

  example 6 to 8, especially 6.

  Particularly preferred in the compositions according to the invention are the alcohols

  in formula III described below.

  The α- (hydroxyphenyl) alkanols of formula IV can be prepared by known methods or by analogy therewith. Thus, the compounds of formula IV can be obtained by the process described in US Pat. -A-4,260,832 or by a method

  analogous to this In this process, 2,6-phenols

  Suitable disubstituted compounds are reacted in the presence of an alkali metal, alkali metal hydroxides or alkoxides at temperatures of 200 to 300 ° C, with removal of the water formed during the reaction with

c, O) -alkanediols.

  The product can then be isolated by conventional methods and used for reaction with the carboxylic acid derivatives of formula V; however, it is also possible to directly use the crude product without further purification, for the preparation of compounds of formula I. If instead of the starting phenols described in US Pat. 832, a 2,6-disubstituted phenol, among which substituents the alkyl group or

  cycloalkyl is not or is at most a group tert-

  butyl, it is possible to obtain new compounds corresponding to the formula III OH Gl G 1

I, (III)

(CH 2) OH

  in which G 'and G' have the indicated meanings

  above for R 1 and R 1 ', the meaning "group tert-

  Butyl is, however, excluded for G 1 As defined above for formula I, N represents an integer between 4 and 8. A compound of formula III is also one of the objects of the invention. compounds of formula III in which Gl 'denotes a secondary or tertiary C 3 -C 24 alkyl group or C 5 -C 8 cycloalkyl; and G 1 denotes a C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl group; It is particularly preferred that G 1 'denotes a secondary or tertiary C 3 -C 18 alkyl group or a C 5 -C 8 cycloalkyl group, for example an isopropyl, sec-butyl, tert-butyl or cyclohexyl group, and G' an alkyl group. C 3 -C 8 with the exception of the tert-butyl group, or a C 5 -C 8 cycloalkyl or a

methyl group.

  Compounds of the formula III in which G 1 denotes a methyl or cyclohexyl group, in particular a methyl group, and G 1 'denote a tert-butyl or cyclohexyl group, in particular, are preferred.

particularly tert-butyl.

  Compounds of formula III in which m is a number from 5 to 8, are preferred.

  example 6 to 8, especially 6.

  Other processes by which or in an analogous manner to which compounds of formula III and compounds of formula IV may be prepared

  described or reported in DE-A-2 147 544 and the NL-

A-79-05000.

  As has been described above, the radical A of formula I derived from a monocarboxylic acid I 1 can be here aromatic, aliphatic, mixed

  aromatic / aliphatic, cycloaliphatic or bicyclic

  aliphatics, or their unsaturated derivatives, for example the following acids: caprylic, acetic, stearic, polyisobutenylsuccinic, n-hexacosanic, trimethylacetic, propionic, isovaleric, lauric, oleic, acrylic, methacrylic, sorbic, linoleic, maleic, itaconic, glutaconic, diacids such as oxalic acid, succinic, isododecylsuccinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic, polymers of fatty acids such as dimers and trimers thereof, of the type described for example in Ind. and Eng Chem 33, 86-89 (1941), of acids containing

  heteroatoms, such as, for example, nitrilo

  triacetic acid, cycloaliphatic acids such as

  cyclohexane carboxylic acid, 1,2 and 1,4-

  cyclohexa-dicarboxylic and naphthenic acids, among which for example cyclopentane acid;

  carboxylic acid, cyclopentylacetic acid, 3-

  methylcyclopentylacetic acid, camphoric acid, 4-

  methylcyclohexane carboxylic acid and 2,4,6-

  trimethylcyclohexane carboxylic acid, the bicyclo

  (2,2,2) -octa-5-ene-2,3-dicarboxylic acid and the bicyclo

  (2,2,1) -hepta-5-ene-2-carboxylic acid, carboxylic acids

  aromatics such as benzoic acid, o-, m-

  and p-toluic acid, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,4,5-benzenetetracarboxylic acid, diphenic acid, 1-naphthoic acid, 2-naphthoic acid, the acid

  naphthalene-1,8-dicarboxylic acid, 1,4-naphthalene

  dicarboxylic acid, naphthalene-1,4,5-tricarboxylic acid, etc., paraffinic oarylacids such as

  phenylacetic acid, hydrocinnamic acid, phenyl

  butyric acid, 7- (1-naphthyl) -butyric acid, α-phenylenenvaleric acid, 9-phenyl-n-caproic acid, diacetic o-, m or pphenylenes or o-acid phenylacetic-g-propionic acid, as well as unsaturated phenyl acids such as, for example, cinnamic acid. A preferred objective of the invention is represented by the compounds corresponding to the formula Ia OH

(CH 3) 3 C R 1

v (Ia)

(CH 2) O C A

  wherein N is an integer from 4 to 8 and m is an integer from 1 to 3, A in the case where om is 1, represents a C 1 -C 2 alkyl group which is unsubstituted or substituted by a C 5 -C 8 cycloalkyl group, or it is a C 2 -C 25 alkyl group which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of the groups -S-, - O and / or -NR 2-, or A, when m is 1, denotes a C 5 -C 8 cycloalkyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 alkenyl group. -C 12, a C 6 -C 8 cycloalkenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group, phenyl, which is unsubstituted or substituted by an alkyl group C 1 -C 12 alkenyl, naphthyl, which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl, biphenyl, which is unsubstituted or substituted by group C 1 -C 12 alkyl or C 2 -C 12 alkenyl, or C 2 -C 25 alkenyl, C 6 -C 10 bicycloalkenyl, C 7 -C 12 phenylalkyl, C 7 -C 12 phenylalkenyl , C1-C16 naphthylalkyl, C1-C16 naphthylalkenyl, C13-C18 biphenylalkyl, C13-C18 biphenylalkenyl or a group of formula II: R4

-CH 2CH 2 OH

  (II), R 3 A, when m is 2, denotes a direct bond, C 1 -C 12 alkylene, C 2 -C 12 alkenylene, C 5 -C 8 cycloalkylene which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group, a C 6 -C 8 cycloalkenylene group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group , a C 6 -C 10 bicycloalkenylene group, phenylene, naphthylene or a C 2 -C 18 alkylene group interrupted by a C 5 -C 8 cycloalkylene or phenylene group or by at least one of the groups -S-, -00 or -NR 2-; A, when m is 3, denotes a group (C 1 -C 8 alkane) triyl, (C 2 -C 8 alkene) triyl, benzenetriyl, naphthalenetriyl; a trivalent group responding to the

R 6

  formula -R 5 -N-R 7 or a group (C 2 -C 18 alkane) triyl, which is interrupted by at least one member of the group -S-, -O or -NR 2; R 1 represents a methyl or tert-butyl group; R 2 represents an H atom or a C 1 -C 4 alkyl group; R 3 and R 4 denote independently of one another a C 1 -C 4 alkyl group, and R 5, R 6 and R 7 independently of one another represent a lower alkylene group;

Cl-C 3 -

  Preferred compounds of formula I are those wherein N is an integer of 4 to 8 and m is an integer of 1 to 4; A, when m is 1, represents a C 1 -C 25 alkyl group which is unsubstituted or substituted by a C 5 -C 8 cycloalkyl group; or it represents a C 2 -C 25 alkyl group which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of the groups -S-, -O and / or -NR 2; or A, in the case where m is 1, denotes a C 5 -C 8 cycloalkyl group, which is unsubstituted or substituted by a C 1 -C 12 alkyl group; a C 6 -C 8 cycloalkenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; a phenyl group which is unsubstituted or substituted by a C1-C12 alkyl group; or a C 2 -C 25 alkenyl group; a C 7 -C 12 phenylalkyl group; or a group corresponding to Formula II No. 4

-CH 2 CH 2 OH

R 3 (II);

  R 3 A, when m is 2, denotes a direct bond; a C 1 -C 12 alkylene group; C 2 -C 12 alkenylene; C 5 -C 8 cycloalkylene, which may be unsubstituted or substituted by C 1 -C 12 alkyl; a C 6 -C 8 cycloalkenylene group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; a phenylene group; a divalent heterocyclic radical selected from furan, thiophene or pyrrole, which is saturated on the nitrogen atom by the hydrogen atom or the substituent -R 2; or A, when m is 2, denotes a C 2 -C 18 alkylene group interrupted by a C 5 -C 8 cycloalkylene or phenylene group or by at least one of -S-, -O or -NR groups 2; and A, when m is 3, denotes a C 1 -C 8 alkane triyl group; a C 2 -C 8 alkene triyl group; a benzotriyl group; a trivalent group having the formula -R 5-k-R 7; or a C 2 -C 18 alkane triyl group which is interrupted by at least one of -S-, -O or -NR 2; A, when m is 4, denotes a benzene or cyclohexyl radical having four free valences; R 1 and R 1 'independently of one another represent a C 1 -C 1 4 alkyl group or a C 5 -C 8 cycloalkyl group; R 2 represents an H atom or a C 1 -C 4 alkyl group; R 3 and R 4 denote independently of one another a C 1 -C 4 alkyl group; and R 5, R 6 and R 7 independently of one another

a C 1 -C 3 alkylene group.

  The compound of formula I wherein R "'is tbutyl or cyclohexyl and R 1 is methyl, tert-butyl or cyclohexyl, n is a number from 4 to 6, and A when m is 1, denotes a C 6 -C 18 alkyl or C 2 -C 12 alkenyl group; A, when m is 2, denotes a direct bond, a C 1 -C 12 alkylene group; phenylene; s / S or a group; C 2 -C 36 alkylene interrupted by 1 to 5 oxygen or sulfur atoms; A, when m is 3, denotes a benzenetriyl CH 2 group or a trivalent group corresponding to the formula -CH 2 -N- CH 2, and A, when m is 4, denotes a benzene radical having 4 free valences, constitutes an object

particularly preferred.

  Among these, compounds of particular importance are those in which A, when m is 1, denotes a C 2 -C 12 alkenyl group; and A, in the case where m is 2, denotes a phenylene group; /; a C 2 -C 36 alkylene group interrupted with 1 to 5 oxygen atoms; or a group - (CH 2) k-S- (CH 2) k; and k is an integer from 1 to 3; and in particular compounds in which m is 1 or 2. Compounds of formula I in which N is an integer of 5 to 8, in particular 6 to 8, are also particularly preferred.

mainly 6.

  Of the compounds of formula I, compounds which stand out particularly are those having the formula

HO OH

CH 3 C (CH 3) 3 CH 3 u C (CH 3) 3 O-, 0

II II

(CH 2) 6-OC A C (CH 2) 6

  wherein A is - (CH 2) j; - (CH 2) k - S - (CH 2) k - / - or - (CH 2) 20 - 1 (CH 2) 2 - O - (CH 2) 2; j is 0 or an integer between 1 and 4; and k denotes a

integer between 1 and 3.

  Compounds having a predominant importance are in particular the following:

  a) 6- (3-tert-butyl-4-hydroxy-5- stearate)

methylphenyl) hexyl;

  b) 6- (3,5-di-tert-butyl-4-hydroxy) stearate

phenyl) hexyl;

  c) succinate bis-1 6- (3-tert-butyl-4-hydroxy-5-

methylphenyl) hexyl;

  d) bis-1 6- (3-tert-butyl-4-hydroxy-5-) adipate

methylphenyl) hexyl;

  e) the bis-1 6- (3-tert-butyl-4-hydroxy-5-

methylphenyl) hexyl;

  f) bis-1-6- (3-tert-butyl-4-hydroxy-5-) isophthalate

methylphenyl) hexyl;

  g) bis-1 6- (3,5-di-tert-butyl) -4-isophthalate

  hydroxyphenyl) hexyl; h) tris-1 6- (3-tertbutyl-4-hydroxy-methylphenyl) hexyl trimellitate;

  j) Tris-1-6- (3,5-di-tert-butyl-4- trimellitate

hydroxyphenyl) hexyl;

  k) tris-1-6- (3-tert-butyl-4-hydroxy-trimellitate)

5-methylphenyl) hexyl;

  1) Tris-l 6- (3,5-di-tert-butyl) -4-trimesinate

  hydroxyphenyl) -hexyl corresponding to the formulas

OH OH

(t I CH 2) OC 73 C CC 17 H 35

C 3 C (CH 3) 3 CCH 3 ó> (CH 3) 3 C ()

OC 26 as 2 C (H)

  (CH 2) 0 C C 7 H 35 (CH 2) C C 17 H 35

6 6

HO OH

CH 3 C (CH 3) 3 CH 3 C (CH 3) 3

OCH 2) 6 -C (CH 2) 6-C-O - (6 (c); O

(CH 2) 6 O C - (CH 2) 27 C O - (CH 2) 6

HO OH

CH 3 / C (CH 3) 3 CH 3 C (CH 3) 3

O O

(CH) C CH 2) 4 O - (CH 2) 6

OH HO

CH 3 C (CH 3) 3 CH 3 C (CH 3) 3

CH 3 "C (CH 2) I (e_);

) CO-C)

(CH 2) 6O C- (CH 2) 6 CO - (CH 2) 6

OH OH

(CH 3) 3 C OCH 3 (CH 3) 3 C

(CH 2) 60-C v C) OH

(CH 3) 3 C.

(CH 3) 3 C CH 3

(CH 2) 6O C

OH

(CH 3) 3 C C (CH 3) 3

(CH 2) 6O-C

OH OH CH 3 (h); CH 3

(CH 3) 3 C

OH

C (CH 3) 3

CH 3 (f);

C (CH 3) 3

(G);

C (CH 3) 3

(); OH

C (CH 3) 3

(CH 3) 3 C

OH

(CH 3) 3 C (S CH 3

(CH 2) 6 o 1 C

(CH) 6 O D C

(K); "CH 3 OH

(CH 3) 3 C

(CH 3) 3 C

C (CH 3) 3

() O O

(CH 2) 6O C

(CH 3) 3 C

  Compounds of particular technical importance are the compounds of formula I, wherein N is an integer of 4 to 6; especially those wherein N is an integer from 4 to 6 and wherein A, when m is 1, denotes a C 6 -C 20 alkyl group, A, when m is 2, denotes a bond direct, a C1-C10 alkylene, phenylene, or C 2 -C 6 alkylene interrupted by -S-, and A, in the case of om is 3, denotes a group

benzenetriyl.

  A preferred object of the invention is furthermore constituted by the compounds corresponding to formula I in OH CH 3

C (CH 3) 3

OH

C (CH 3) 3

  (1). m is 2 and A is alkylene

  C 4 -C 36 interrupted by at least one oxygen atom.

  Compounds of formula I of interest are furthermore those in which A, when m is 1, denotes a C 6 -C 20 alkyl group; C 3 -C 18 alkenyl; C 6 -C 36 alkyl interrupted by one or more of -S or -O-, cyclohexyl, cyclohexyl substituted by C 1 -C 4 alkyl, phenyl, phenyl substituted by a C 1 -C 12 alkyl group or a phenylalkyl group having a total of 7 to 9 carbon atoms; A, in the case where om is 2, denotes a direct bond, a C 1 -C 12 alkylene group, C 2 -C 12 alkenylene, phenylene or C 2 -C 36 alkylene interrupted by a -S group or -O-, and A, when m is equal to 3, denotes a group (C 1 -C 8 alkane) triyl, benzenetriyl, C 7 -C 10 alkylbenzenetriyl, CH 2

* or -CH 2-N-CH 2-.

  The compounds of formula I are suitable for the stabilization of organic materials with respect to thermal, oxidative and actinic degradation; we must insist in particular on the remarkable action as

  antioxidants in the stabilization of organic matter.

  Examples of such materials are: Polymers of mono and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and cycloolefin polymers such as for example those of cyclopentene or norbornene; and also polyethylene (which may optionally be crosslinked), for example high density polyethylene (P Ehd), low density polyethylene (P Ebd), linear low density polyethylene (LDPE),

  low density branched polyethylene (PE Rbd).

  Polyolefins, that is to say polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, may be prepared by various processes, in particular by the processes following: a) radical (usually under high pressure and high temperature); b) using a catalyst, the catalyst usually containing one or more metals of groups I Vb, Vb, V Ib or VIII These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyl, alkenyl and / or aryl radicals which can be coordinated either by X bonds or by C bonds These metal complexes can be free or supported on a support, for example on activated magnesium chloride, These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or it can be used. other activators such as, for example, alkyl metals, metal hydrides, alkyl metal halides, alkyl metal oxides or alkyloxane metals, the metals being For example, the activators may be modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually known as Phillips, Standard Oil Indiana catalysts. , Ziegler (-Natta), TNZ (Dupont), metallocene or single site catalysts

(SSC).

  Mixtures of the polymers indicated in 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / P Ehd, PP / P Ebd) and mixtures of various

  types of polyethylenes (eg P Ebd / P Ehd).

  Copolymers of mono and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (P Ebd) and mixtures thereof with low density polyethylene (P); Ebd),

  propylene-butene-1 copolymers, propylene-

  isobutylene, ethylene-butene-1 copolymers,

  ethylene-hexene copolymers, ethylene-

  methylpentene, ethylene-heptene copolymers,

  ethylene-octene copolymers, propylene-

  butadiene, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, copolymers

  ethylene-alkyl methacrylate, ethylene-

  vinyl acetate and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), as well as tert-polymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and further blends of these copolymers with each other and with the polymers indicated in 1, for example propylene / ethylene-propylene copolymers, Ebd / ethylene-vinyl acetate copolymers, Ebd / ethylene-acrylic acid copolymers, LDPE / ethylene-vinyl acetate copolymers, Lbd / ethylene-acrylic acid copolymers and alternating or random copolymers of polyalkylene / carbon monoxide and mixtures thereof with other polymers, for example polyamides. Hydrocarbon resins (for example C 5 -C 8), including their hydrogenated variants (with adhesive resins) and mixtures of polyalkylenes and starch. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene). Copolymers of styrene or c-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene-butadiene, styrene-acrylonitrile,

  styrene-alkyl methacrylate, styrene-butadiene-

  alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; mixtures with high impact strength of copolymers of styrene and another polymer, such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as copolymers

  styrene blocks, such as, for example, styrene

  butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene or styrene-ethylene / propylene-styrene.

  Graft copolymers of styrene or

  methylstyrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and

  acrylonitrile on ethylene-propylene terpolymers

  diene, styrene and acrylonitrile on alkyl polyacrylates or alkyl polymethacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their blends with the copolymers indicated in 6), which are known from example under the names of polymers

ABS, MBS, ASA or AES.

  Halogenated polymers, such as for example polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo and copolymers of epichlorohydrin, in particular polymers of compounds halogenated vinyls, such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; as well as their copolymers, such as

  Vinyl-vinylidene chloride, vinyl chloride

  vinyl acetate or vinylidene chloride-vinyl acetate. Copolymers derived from%, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates modified to increase their impact resistance by butyl acrylate, polyacrylamides and polyacrylonitriles. Copolymers of the monomers indicated in 9), with each other or with other unsaturated monomers such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile copolymers vinyl halide or

  acrylonitrile-alkyl methacrylate terpolymers

  butadiene. Polymers derived from alcohols and unsaturated amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyacetate, stearate, benzoate, polyvinyl maleate, polyvinyl butyral, allyl polyphthalate polyallylmelamine; as well as their copolymers with

olefins indicated in point 1).

  Homo and copolymers of cyclic ethers such as polyalkylene glycols, polyoxyethylenes, polyoxypropylenes or copolymers thereof with bisglycidyl ethers. Polyacetals, such as polyoxymethylene, as well as polyoxymethylenes which contain comonomers, such as ethylene oxide; polyacetals which are modified by thermoplastic polyurethanes,

acrylates or MBS.

  Polyphenylene oxides and sulfides and their

  mixtures with styrene polymers or polyamides.

  Polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups, on the one hand, and aliphatic or aromatic polyisocyanates, on the other hand, and their

intermediate products.

  Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, such as polyamide 4, polyamide 6, polyamides 6/6, 6/10, 6/9 , 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained from m-xylene, a diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso and / or terephthalic acids and, where appropriate,

  elastomer as a modifier, for example poly-2,4,4-

  trimethylhexamethylene terephthalamide or poly-m-

  phenylene-isophthalamide Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol And also with polyamides or copolyamides modified with EPBM or ABS; as well as condensed polyamides during processing

(polyamide "RIM" systems).

  Polyureas, polyimides, polyamide-imides

and polybenzimidazoles.

  Polyesters derived from dicarboxylic acids and dialcohols, and / or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutyleneterephthalate, poly-1,4-dimethylolcyclohexaneterephthalate, polyhydroxybenzoates and polyether esters sequences derived from polyethers having hydroxyl end groups, and also polyesters modified with

polycarbonates or MBS.

  Polycarbonates and polyester carbonates.

  Polysulfones, polyether sulfones and polyether ketones. Crosslinked polymers which are derived from aldehydes and from phenols, urea or melamine, such as phenol-formaldehyde resins,

  urea-formaldehyde and melamine-formaldehyde.

  Drying or non-drying alkyd resins.

  Unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyalcohols, as well as vinyl compounds as crosslinking agents, and also their variants

halogenated, not very combustible.

  Crosslinkable acrylic resins derived from substituted acrylic esters, such as, for example,

  epoxy acrylates, urethane acrylates or poly-

  ester acrylates. Alkyd resins, polyester resins and acrylate resins which are cross-linked with

  melamine resins, urea resins, poly-

isocyanates or epoxy resins.

  Crosslinked epoxy resins derived from polyepoxides, for example bis-glycidyl ethers or

cycloaliphatic diepoxides.

  Natural polymers, such as cellulose, natural rubber, gelatin and their homologous derivatives of chemically modified polymers, such as cellulose acetates, propionates and butyrates or cellulose ethers such as methylcellulose; and

  also rosin resins and their derivatives.

  Mixtures (Polyblends) of the foregoing polymers, such as for example PP / EPDM, polyamide / EPDM or

  ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA,

  PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS,

  PPO / PA 6-6 and copolymers, PA / P Ehd, PA / PP, and PA / PPO.

  29 Natural and synthetic organic substances which constitute pure monomeric compounds or mixtures thereof, for example mineral oils, animal or vegetable fats, oils or waxes, or synthetic ester oils, greases and waxes (eg phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any weight ratios, as used as spinning preparations, as well as their aqueous emulsions . Aqueous emulsions of natural or synthetic rubbers, such as a natural rubber latex or

  carboxylated styrene / butadiene copolymer latexes.

  Other objects of the invention are therefore compositions containing an organic material sensitive to oxidative, thermal and / or actinic degradation and at least one compound corresponding to formula I, as well as the use of compounds corresponding to the formula I for the stabilization of an organic material against

  oxidative, thermal or actinic degradation.

  The invention therefore also comprises a method for stabilizing an organic material against thermal, oxidative and / or actinic degradation, characterized in that at least one compound corresponding to formula I is added to this material. of compounds of formula I as antioxidants in organic polymers

  synthetic is of particular interest.

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

  a polyolefin or a copolymer of styrene.

  In general, the compounds corresponding to formula I are added to the material to be stabilized in amounts of from 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% relative to total weight of the material to be stabilized It is particularly preferred to use the compounds according to the invention in amounts of

  0.01 to 0.5%, more preferably 0.05 to 0.3%.

  In addition to the compounds corresponding to formula I, the compositions in accordance with the invention may also contain conventional additives, such as for example those

indicated below.

  1 Antioxidants 1.1 Alkylated monophenols, for example: 2,6-ditert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 -di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (amethylcyclohexyl) -4,6-dimethylphenol, 2,6 -dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- ( 1 '-methyl-undec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1-methyl) -2-dimethyl-6- (1'-methyl-heptadec-1-yl) phenol, tridec-l-yl) -phenol and

mixtures thereof.

  Alkylthiomethylphenols, for example: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-tert-methylphenol, 2,4-dioctylthiomethyl-6-tert-ethylphenol and 2,6-di-dodecylthiomethyl-4nonylphenol. 1 3 Hydroquinones and alkylated hydroquinones, by

example:

  2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-ditert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl stearate 4hydroxyphenyl and

  bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

  1.4 Hydroxy thiodiphenyl ethers, for example 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-tertbutyl-2-methylphenol), 4,4'-thio-bis- (3,6-di- sec-amylphenol) and

  4,4'-bis- (2,6-dimethyl-4-hydroxy) disulfide

  phenyl). 1.5 Alkylidene-bis-phenols, for example: 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), \

  2,2'-methylene-bis-1,4-methyl-6- (α-methylcyclohexyl) -

  phenoll, 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4-methyl- 6-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol), 2,21'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol),

  2,2'-methylene-bis-1-6- (α-methylbenzyl) -4-nonyl

phénoll,

  2,2'-methylene-bis-1-6- (α, α-dimethylbenzyl) -4-nonyl

  phenoll, 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol),

  1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl)

butane,

  2,6-bis- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-

methylphenol

  1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl)

butane,

  1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-

dodecylmercapto-butane,

  Ethylene glycol-bis-3,3-bis- (3'-tert)

butyl-4'-hydroxyphenyl) 1,

  bis- (3-tert-butyl-4-hydroxy-5-methylphenyl)

dicyclopentadiene

  bis-1 2- (3'-tert-butyl-2'-hydroxy-5 'terephthalate

  methylbenzyl) -6-tert-butyl-4-methylphenyl, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -propane,

  2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-

dodecylmercapto-butane and

  1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methyl)

  phenyl) -pentane, 1.6 Oxygen, nitrogen and S-benzyl compounds, by

example:

  3,5,3 ', 5'-tert-butyl-4,4'-dihydroxy ether

  dibenzyl, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -amine,

  bis (4-tert-butyl-3-hydroxy) dithioterephthalate

  2,6-dimethylbenzyl), bis- (3,5-di-tert-butyl-4hydroxybenzyl) sulfide and

  3,5-di-tert-butyl-4-hydroxy-mercaptoacetate

  benzyl). 1.7 Hydroxybenzyl malonates, for example: dioctadecyl 2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate dioctadecyl, dodecylmercaptoethyl 2,2-bis- (3,5di-tert-butyl-4-hydroxybenzyl) -malonate and 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate

  di-1- 4- (1,1,3,3-tetramethylbutyl) phenylel.

  1.8 Hydroxybenzyl aromatic hydrocarbons, by

example:

  1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -

2,4,6-trimethyl benzene,

  1,4 bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-

tetramethylbenzene and

  2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -

  phenol. 1 9 Triazine compounds, for example:

  2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-

hydroxyanilino) -1,3,5-triazine,

  2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-

hydroxyanilino) -1,3,5-triazine,

  2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-

hydroxyphenoxy) -1,3,5-triazine,

  2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -

1,2,3-triazine

  1,3,5-tris- (3,5-di-tert-butyl) -4-isocyanurate

hydroxybenzyl)

  isocyanurate of 1,3,5-tris- (4-di-tert-butyl-3-

hydroxy-2,6-dimethylbenzyl)

  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-hydroxyphenyl)

  propionyl) -hexahydro-1,3,5-triazine and

  isocyanurate of 1,3,5-tris- (3,5-dicyclohexyl-4-

  hydroxybenzyl). 1.10 Benzyl phosphonates, for example:

  dimethyl-2,5-di-tert-butyl-4-hydroxyphosphonate

benzyl,

  diethyl-3,5-di-tert-butyl-4-hydroxyphosphonate

benzyl,

  dioctadecyl-3,5-di-tert-butyl-4- phosphonate

hydroxybenzyl,

  dioctadecyl-5-tert-butyl-4-hydroxy-3- phosphonate

methylbenzyl and

  Ca salt of the monoethyl ester of 3,5-

  di-tert-butyl-4-hydroxybenzyl-phosphonic acid. 1 11 Acylaminophenols, for example: 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide and

  octyl ester of N- (3,5-di-tert-butyl-4-)

hydroxyphenyl) -carbamic.

  1.12 Esters of Z- (3,5-di-tert-butyl-4-) acid

  hydroxyphenyl) -propionic with mono or poly-alcohols, for example:

  methanol, ethanol, octadecanol, 1,6-

  hexane-diol, 1,9-nonane-diol, ethylene glycol,

  1,2-propanediol, neopentylglycol, thio-

  diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,

  tris (hydroxyethyl) isocyanurate, N, N'-bis-

  (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,

  trimethylolpropane and 4-hydroxymethyl-1-phospha-

  2,6,7-trioxabicyclo [1,2,2] 1-octane.

  1.13 Esters of Z- (5-tert-butyl-4-hydroxy-3-) -acetate

  methylphenyl) -propionic with mono or poly-alcohols, for example:

  methanol, ethanol, octadecanol, 1,6-

  hexane-diol, 1,9-nonane-diol, ethylene glycol,

  1,2-propanediol, neopentylglycol, thio-

  diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,

  tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol,

trimethylhexane-diol, the

  trimethylolpropane and 4-hydroxymethyl-1-phospha-

  2,6,7-trioxabicyclo [1,2,2] 1-octane.

  1.14 Esters of B- (3,5-dicyclohexyl) -4-acid

  hydroxyphenyl) -propionic with mono or poly-alcohols, for example:

  methanol, ethanol, octadecanol, 1,6-

  hexane-diol, 1,9-nonane-diol, ethylene glycol,

  1,2-propanediol, neopentylglycol, thio-

  diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,

  tris (hydroxyethyl) isocyanurate, N, N'-bis-

  (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,

  trimethylolpropane and 4-hydroxymethyl-1-phospha-

  2,6,7-trioxabicyclo [1,2,2] 1-octane.

  Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono or polyalcohols,

for example:

  methanol, ethanol, octadecanol, 1,6-

  hexane-diol, 1,9-nonane-diol, ethylene glycol,

  1,2-propanediol, neopentylglycol, thio-

  diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,

  tris (hydroxyethyl) isocyanurate, N, N'-bis-

  (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane-diol,

  trimethylolpropane and 4-hydroxymethyl-1-phospha-

  2,6,7-trioxabicyclo [1,2,2] 1-octane.

  1.16 3- (3,5-di-tert-butyl) -acid amides

  hydroxyphenyl) -propionic, for example:

  N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenyl)

propionyl) -hexamethylene-diamine,

  N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenyl)

  propionyl) -trimethylene diamine and

  N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenyl)

propionyl) -hydrazine.

  2 UV absorbers and light-protecting agents 2.1 2- (2'-Hydroxyphenyl) -benzotriazoles, for example: 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole,

  2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzoate

  triazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole,

  2- (2'-Hydroxy-5 '- (1,1,3,3-tetramethylbutyl) -phenyl) -

benzotriazole,

  2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro

benzotriazole,

  2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-

chloro-benzotriazole,

  2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -

  benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole,

  2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) -benzoate

triazole,

  2- (3 ', 5'-bis (, α-dimethylbenzyl) -2'-hydroxyphenyl) -

benzotriazole,

  a mixture of 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-

  octyloxycarbonyléthyl) -phenyl) -5-chloro-benzo

triazole,

  2- (3'-tert-butyl-5'-l 2- (2-ethylhexyloxy) -carbonyl)

  ethyl-2'-hydroxyphenyl) -5-chloro-benzotriazole,

  2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl)

  ethyl) phenyl) -5-chloro-benzotriazole,

  2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl)

ethyl) phenyl) benzotriazole,

  2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonyl)

ethyl) phenyl) benzotriazole,

  2- (3'-tert-butyl-5'-l 2- (2-ethylhexyloxy) -carbonyl)

  ethyl) -2'-hydroxyphenyl) -benzotriazole,

  2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzoate

triazole and

  2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxy)

  carbonylethyl) phenyl) benzotriazole,

  2,2'-Methylenebis-4- (1,1,3,3-tetramethylbutyl) -6-

benzotriazol-2-yl-phénoll,

  product of the transesterification of 2- (3 '-tert-

  butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-

phenyl benzotriazole with polyethylene glycol 300,

  lR-CH 2 CH 2 -COO (CH 2) 3 1 2 with R = 3'-tert-butyl-4 '-

  5'-hydroxy-2H-benzotriazol-2-yl-phenyl.

  2 2 2-Hydroxybenzophenones, for example: 4-hydroxyl, 4methoxylated, 4-octyloxylated, 4-decyloxylated, 4-dodecyloxylated, 4-benzyloxylated derivatives,

  4.2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy.

  2.3 Esters of optionally substituted benzoic acids, for example: 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl-resorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoyl-resorcinol,

  2,4-di-tert-butyl-4-hydroxybenzoate 3,5-di-tert-butyl-4-hydroxybenzoate

  hexadecyl butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and

  3,5-di-tert-butyl-4-hydroxybenzoate-2-methyl-4,6-di-

  tert-butylphenyl. 2.4 Acrylates, for example: c-cyano-Z, ethyl diphenylacrylate, isocyanoyl-cyano-, 1-iso-octyl-diphenylacrylate, methyl-α-methoxycarbonyl-cinnamate, c-cyano-β-methyl-pmethoxy- methyl cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-methoxycarbonyl-p-methoxy-cinnamate and

  N- (methoxycarbonyl-B-B-cyanovinyl) -2-methylindoline.

  2.5 Nickel compounds, for example:

  nickel complexes derived from 2,2'-thio-bis-1-4

  (1,1,3,3-tetramethylbutyl) -phenoll, for example the 1: 1 complex or the 1: 2 complex, optionally with other ligands, such as n-butylamine, triethanolamine or N-cyclohexyl- diethanolamine, nickel dibutyl-dithiocarbamate, nickel salts of alkyl monoesters of

  4-hydroxy-3,5-di-tert-butyl-benzyl-

  such as methyl and ethyl esters, nickel complexes derived from ketoximes, such as 2-hydroxy-4-methyl-phenylundecylketoxime, and

  nickel complexes of 1-phenyl-4-lauroyl-5-

  hydroxypyrazole, possibly with

additional coordinators.

  2.6 Hindered amines, for example: bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis- (1,2,2) sebacate, 6,6 -pentamethylpiperidyl), bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate,

  condensation product of 1-hydroxyethyl

  2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid,

  condensation product of N, N'-bis- (2,2,6,6-

  tetramethyl-4-piperidyl) -hexamethylenediamine with 4-tert-octylamino2,6-dichloro-1,3,5-triazine,

  tris nitrilotriacetate (2,2,6,6-tetramethyl-4-

piperidyl) sebacate,

  Tetrakist 1,2,3,4-butane tetracarboxylate

  (2,2,6,6-tetramethyl-4-piperidyl)

  1,1 '(1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl)

  piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine,

  bis-1,2,2,6,6-4-pentamethylpiperidyl malonate) -2-

  n-butyl- (2-hydroxy-3,5-di-tert-butylbenzyl)

  3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-

1,4-decane-2,4-dione,

  bis- (1-octyloxy-2,2,6,6-tetramethyl) sebacate

piperidyl) sebacate,

  bis- (1-octyloxy-2,2,6,6-tetramethyl) succinate

piperidyl) sebacate,

  condensation product of N, N'-bis- (2,2,6,6-bis)

  tetramethyl-4-piperidyl) -hexamethylenediamine with 4-morpholino-2,6dichloro-1,3,5-triazine,

  condensation product of 2-chloro-4,6-di- (4-n-

  butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5

  triazine with 1,2-bis- (3-aminopropylamino) -

  ethane, a condensation product of 2-chloro-4,6-di- (4-n-

  butylamino-1,2,2,6,6-pentaméthylpipéridyl) -1,3,5

  triazine with 1,2-bis- (3-aminopropylamino) -

ethane,

  8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8

  triazaspiro-1,4-decane-2,4-dione,

  3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl)

pyrrolidine-2,5-dione and

  3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl)

  pyrrolidine-2,5-dione, 7 Oxalamides, for example: 4,4'-dioctyloxyoxalanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxalanilide, 2,2'-didodecyloxy-5, 5'-di-tert-butyl-oxalanilide, 2-ethoxy-2'-ethyloxalanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxalanilide,

  mixtures thereof with 2-ethoxy-2'-ethyl-

, 4'-tert-butyl-oxalanilide and

  mixtures of 2,2'-dimethoxy and 4,4'-dimethoxy

  oxalanilides as well as 2,2'-diethoxy and 4,4'-

  diethoxy-oxalanilides. 2.8 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example:

  2,4,6-tris- (2-hydroxy-4-octyloxyphenyl) -1,3,5-

triazine

  2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-

dimethylphenyl) -1,3,5-triazine,

  2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-

dimethylphenyl) -1,3,5-triazine,

  2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-

dimethylphenyl) -1,3,5-triazine,

  2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (4-methyl)

phenyl) -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-butyloxypropyloxy)]

  phenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and

  2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy)]

  phenyll-4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 3 Metal deactivators, for example: N, N'-diphenyl oxalamide, N-salicylidene N'-salicyloyl hydrazine, N, N'-bis-salicyloyl hydrazine,

  N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl)

  propionyl) -hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene hydrazide) oxalic acid, oxanilide, isophthalic acid dihydrazide, bis-phenylhydrazide sebacic acid, dihydrazide N, N'-diacetal-adipic acid, N, N'-bis-salicyloyl-oxalic acid dihydrazide and

  di-hydrazide of N, N'-bis-salicyloyl

  thiopropionic. 4 Other phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, phosphite tris (2,4-di-tert-butylphenyl), diisodecylpentaerythritol diphosphite,

  Bis (2,4-di-tert-butyl-phenyl) diphosphite

pentaerythritol

  diphosphite of bis- (2,6-di-tert-butyl-4-

  methylphenyl) -pentaerythritol, diphosphite of bis- (isodecyloxypentaerythritol,

  diphosphite of bis- (2,4-di-tert-butyl-6-methyl-

phenyl) pentaerythritol,

  Bis (2,4,6-tri-tert-butylphenyl) diphosphite

  pentaerythritol, tristearyl sorbitol triphosphite,

  tetrakis (2,4-di-tert-butylphenyl) diphosphite

4,4'-biphenylene,

  6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-

dibenzld, gl-1,3,2-dioxaphosphocine,

  6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-

dibenzld, gl-1,3,2-dioxaphosphocine,

  Bis (2,4-di-tert-butyl-6-methylphenyl) phosphite

methyl and

  phosphite of bis- (2,4-di-tert-butyl-6-methyl)

  phenyl). Peroxide destroyers, for example: esters of 2-thiodipropionic acid, such as lauryl, stearyl, myristyl and tridecyl esters,

  mercaptobenzimidazole and zinc salts of 2-mercapto

  benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and

  tetrakis- (B-dodecylmercapto) -propionate penta

  erythritol. Stabilizers of polyamides, for example: copper salts associated with iodides and / or phosphorus compounds, and salts of divalent manganese. 7 Basic co-stabilizers, for example: melamine, poly (vinylpyrrolidone), cyanoguanidine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes,

  alkali metal or alkali metal salts

  earthy fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate or potassium palmitate, antimony pyrocatecholate and pyrocatecholate

tin.

  8 Nucleating agents, for example: 4-tert-butyl-benzoic acid, adipic acid and

diphenylacetic acid.

  9 Charges and reinforcing agents, for example: calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black and graphite. Other additives, for example: plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistats and porogens. Benzofuranones or indolinones as described

  in US-A-4,325,863 or US-A-4,338,244.

  Conventional additives are added for example at concentrations of 0.01 to 10% by weight

total of the material to be stabilized.

  The incorporation of the compound corresponding to formula I and, if appropriate, other additives into the material

  organic is carried out by known methods.

  The incorporation into the materials may for example be carried out by mixing or application of the compounds corresponding to formula I and, if appropriate, other

  additives, by methods customary in the art.

  In the case of polymers, in particular synthetic polymers, the incorporation may take place before or during shaping, or by application of the compounds dissolved or dispersed on the polymer, with evaporation

  solvent in the case of elastomers, these

  They can also be stabilized as latex.

  Another possibility of incorporating the compounds corresponding to formula I into the polymers is to add them before, during or immediately after the polymerization of the corresponding monomers or before crosslinking. The compounds corresponding to formula I may be added in this case as they are. , 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 corresponding to formula I may act as regulators of the length of

  chain of polymers (chain breakers).

  The compounds corresponding to formula I can also be used in the form of a masterbatch which contains them for example at a concentration of 2.5 to 25% by weight.

weight, materials to be stabilized.

  The materials thus stabilized can be used in the most diverse forms, for example in the form of sheets, fibers, strips, molding materials, profiles or binders for

  lacquers, adhesives or sealants.

  The following examples are given as a further explanation of the invention. Unless otherwise indicated, the parts and percentages are by weight. In the formulas, the prefix N denotes a linear alkyl radical, the prefix i a mixture of isomers. the "melting point" is abbreviated

by "F".

  EXAMPLE 1a Preparation of 4- (3-tert-butyl-5-

  In an autoclave 50 g of potassium hydroxide, 316 g of 2-tert-butyl-6-methylphenol and 866 g of 1,4-butanediol were introduced. nitrogen, the autoclave is closed and the mixture is heated at 235 ° C. (under 4 bar) with stirring for 6 hours; A further increase of the pressure as a result of the reaction is prevented by allowing gas to escape. When the reaction is complete, it is cooled to 80 ° C. and the autoclave is evacuated. The excess butanediol is removed by distillation. Distillation is poured into 1 liter of water and 500 ml of toluene. The organic phase is then washed until neutral with water and the toluene is removed by applying a vacuum. The residue (310 g) contains the product in question. title corresponding to the formula: OH

(CH 3) 3 C "ACH 3

CH. ,, CH_ OH

  The additional purification is carried out by fractional distillation under vacuum. The crude product boils at C under 35 Pa (= 0.35 mbar).

refraction n D = 1.5322.

  EXAMPLE 1b Preparation of 6- (3-tert-butyl) -5-

  Methyl-4-hydroxyphenyl) -butanol Example 1a is repeated with the difference that instead of 1,4-butanediol, an equivalent amount of 1,6-hexane-diol is used. The product obtained, corresponding to the formula: OH

(CH 3) 3 C CH 3

(CH 2) 6-OH

  it has a boiling point below 35 Pa (= 0.35 mbar)

 C and bottom at 45 C.

EXAMPLE 1c

  To a solution of 18.9 g (80 mmol) of 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) butanol (product of Example 1a) and 9.5 g (120 mmol) of pyridine in 90 ml of toluene, a solution of 25.5 g (84 mmol) of stearic acid chloride in 10 ml of toluene is added dropwise at 10 ° C. under nitrogen. The white suspension is then allowed to warm to 20 ° C. 25 ° C., filtered, the filtrate is poured into about 1M aqueous HCl and extracted with ethyl acetate. After drying and concentration of the organic phase, the crude product obtained is purified by chromatography (SiO 2). 2: hexane: ethyl acetate = 19: 1) 37.2 g (93%) of the product corresponding to the following formula is obtained: OH OH (CH 2) 4 O -C n -C 17 H 35 (compound n 1) in the form of a colorless liquid Characterization (IR) and composition are given in

Table 1.

EXAMPLES 2 TO 16

  For the preparation of compounds 2 to 16, firstly, by synthesis, by the method described in

  Example 1a, o- (3-tert-butyl-5-methyl-4-hydroxy)

  phenyl) alkanols or (o (3,5-di-tert-butyl-4-hydroxy)

  corresponding phenyl) alkanols The starting compounds thus obtained (compounds corresponding to formula IV) are then converted, using the corresponding acid chlorides, by the method described in Example 1c, into the final products indicated (compounds which correspond to in formula (I) The indications as to the purity and

  Characterization of the compounds are shown in Tables 1 and 2. Where no melting point is indicated, the compounds are liquid at room temperature.

TABLE 1

  Compositions and IR data for compounds 1 to 8 Compound type: OH

(CH 3) 3 C / CH 3

(CH 2) T O

I A

(C H 2-) C -A

  Comp NA COMPOSITION IR: 1 / n C%: H: C = O calc found calc found lcmnll 1 4 -nC 17 H 78,8 78,7 11,6 11,4 1738 2 4 -nC 7 H 15 76, 2 76.1 10.6 10.6 1719 3 4 - iC 7 H 15 76.2 76.2 10.6 11.0 1717 4 4 -iC 12 H 25 77.7 77.7 11.2 11.1 1717 4-iC 7 H 15 76.2 76.0 10.6 10.4 1715

C 2 H 5

  6 6 -CH 2-CH-CH 2-C 2 H 576.9 76.9 10.8 10.6 1715

  7 6 -n-Cl 11 H 23 78.0 77.9 11.3 11.5 1732 8 6 -n-C 17 H 35 79.2 79.1 11.8 12.2 1720 (See Table 2 on the next page)

TABLE 2

  M.p. % n lCl C% H: C = O calc found calc found lc-1 l

C 2 H 5

  9 4 -CH 2-CH-CH 2-C 2 H 5 77.2 77.0 11.0 10.8 1732

  4 -nC 7 H 15 77.2 77.2 11, 11.4 1736 11 4 -iC 12 H 25 78.4 78.3 11.5 11.5 1735 12 4-nC 17 H 35 3033 79.4 79 , 5 11.8 12.1 1738 13 5-nC 17 H 35 31-32 79.5 79.6 11.9 11.9 1738

C 2 H 5

  14 6 -CH 2-CH-CH 2-C 2 H 5 77.7 77.7 11.2 11.5 1738

  6-n-Cll H 23 _ 78.6 78.5 11.6 11.9 1737 16 6 -n-C 17 H 35 35 79.7 79.6 12.0 12.2 1738

EXAMPLE 17

  In a 350 ml sulphonation flask, a colorless solution of 33 g (0.14 mol) of the product of Example la and 16.6 g (0.21 mol) of pyridine in 200 ml are added dropwise. toluene, at 10 ° C., under nitrogen, 13.6 g (0.074 mol) of adipic acid dichloride. The mixture is then allowed to warm to ambient temperature while stirring. After 2 hours, the mixture is poured reaction mixture on aqueous hydrochloric acid and extracted with ethyl acetate After drying and concentration of the organic phase, the crude product obtained is purified by chromatography (SiO 2, hexane: ethyl acetate = 19: 1) 36 g (88%) of the product (compound No. 17) corresponding to the formula:

OH OH

0 0

(CH 3) 3 C, CH 3 CH 3> A C (CH 3) 3

He II

(CH 2) 4 O C - (CH 2) 4 C O - (CH 2) 4

  melting at 50-52 C Characterization (IR) and

  composition are given in Table 3.

EXAMPLES 18-22 AND 24-34

  For the preparation of compounds 18 to 22 and 24 to 34, firstly by synthesis, by the method described

  in Example la, Co (3-tert-butyl-5-methyl-4-

  hydroxyphenyl) -alkanol or O (3,5-di-tert-butyl-4-

  corresponding hydroxyphenyl) -alkanols The starting products thus obtained (compounds corresponding to formula IV) are then converted, using the corresponding dicarboxylic acid dichlorides by the process described in Example 1c, into the final products indicated (compounds corresponding to with the formula -I) The indications on the purity and the characterization of the compounds obtained are

  collected in Tables 3, 4 and 5.

EXAMPLE 23

  In a 750 ml sulphonation flask, 4.98 g (30 mmol) of isophthalic acid, 14.4 g (70 mmol = 2.3 equivalents) of dicyclohexylcarbodiimide and 150 ml are mixed under nitrogen at -25 ° C. under nitrogen. of dichloromethane is added the white suspension obtained from a solution of

  9 g (60 mmol = 2 equivalents) of 6- (3-tert-butyl) -5-

  methyl-4-hydroxyphenyl) -hexanol (product of Example 1b) in 80 ml of dichloromethane and a solution of 0.73 g (6 mmol) of dimethylaminopyridine in 5 ml of dichloromethane The mixture is refluxed for 4 hours. It is then cooled to 20 ° C., filtered and evaporated The crude product obtained (viscous oil) is purified by chromatography (SiO 2, hexane / ethyl acetate = 19: 1). 3 g (57%) of compound no. 23 in the form of a colorless oil. Indications of purity and characterization are

given in Table 3.

TABLE 3

  Melting points, compositions and IR data for compounds 17 to 23 Compound type:

OH OH

(CH 3) 3 C CH 3 CH 3 C (CH 3) 3

  (CH 2) f O C A -C - (CH 2) n COMP N A F IR COMPOSITION: 1/1 n o lCl C% H%: C = O calc found calc found lcm-1 l

  17 4 - (CH 2) 4 50-52 74.2 73.8 09.3 09.5 1718

  18 4 - (CH 2) 8 75.2 74.7 09.8 09.9 1717

19 6 74.2 74.1 09.3 09.7 1738

  6 - (CH 2) 2 90-103 74.7 73.9 09.6 09.8 1713

  21 6 - (CH 2) 4 91-95 75.2 75.0 09.8 09.7 1718

  22 6 - (CH 2) 8 76.0 75.5 10.2 10.2 1718

23 6 76.6 76.1 08.9 09.1 1723

(See table 4 next page)

TABLE 4

  Melting point, compositions for compounds

(CH 3) 3 C

Type of compound:

C (CH 3) 3

and data

24 to 30

  of IR OH A -C O- (CH 2) n COMP N A F IR COMPOSITION: 1/1 n l Cl C% H%: C = O calc found calc found lcmn'1 l

  24 4 - (CH 2) 4 86-88 75.6 75.5 10.0 09.8 1734

5 89-90 75.2 75.1 09.8 09.9 1743

  26 5 - (CH 2) 4 92-95 76.0 75.6 10.2 10.0 1735

27 6 75.6 75.7 10.0 10.1 1743

  28 6 - (CH 2) 2 70 76.0 75.9 10.2 10.4 1736

  29 6 - (CH 2) 4 54-57 76.4 76.5 10.3 10.6 1735

6 - (CH 2) 8 77.1 77.1 10.6 10.6 1735

Melting points, for

TABLE 5

  IR compositions and data n 31 to 34

OH OH

(CH 3) 3 C R R 1 C (CH 3) 3

Type of compound:

O O

  II (CH 2) f -O-C - (CH 2) ij S - (CH 2) rC-O (C 2 Comp NR 1) IR COMPOSITION: 1 /, n C%: H%: S%: C = O calc found calc found calc found lcmrll

  31 4 CH 3 2 70.3 70.5 8.9 9.0 5.2 5.4 1731

  32 6 CH 3 2 71.6 71.5 9.3 9.5 4.8 4.9 1732

  33 5 C (CH 3) 3 2 72.7 72.6 9.7 9.7 4.4 4.7 1736

  34 5 C (CH 3) 3 1 72.1 72.0 9.5 9.6 4.6 4.7 1734

EXAMPLE 35

  Example 23 is repeated, with this difference that

  the place of the product of Example 1b, we start from 6- (3,5-di-

  tert-butyl-4-hydroxyphenyl) -hexanol The product (compound 35) having the formula:

OH OH

  (CH 3) 3 c C (CH 3) 3 (CH 3) 3 c C (CH 3) 3 OO II He

(CH 2) 6O O C O - (CH 2) 6

  exhibits an IR absorption of the carbonyl band at 1723 cm -1. Composition: Calc 77.6% C, 9.5% H, Found 77.1% C, 9.5% H.

EXAMPLE 36

  In a round bottom flask equipped with a distillation column, 7.57 g (30 mmol) of trimellitic acid methyl ester, 33 g (117 mmol) of the product of Example 1b and 0, are mixed. 45 g (1.8 mmol) of dibutyltin oxide The mixture is heated to 180 ° C., while distilling off the methanol After 2 hours, the pressure on the mixture is lowered to 533 h Pa (= 400 torr) the temperature is then maintained at 180 ° C. for a further 4 hours.

  the excess of 6- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -

  hexanol by distillation (150 ° C., 4 Pa) and the crude product obtained is purified by chromatography (SiO 2, first hexane, then hexane / ethyl acetate = 19/1). ) a product that meets the formula

OH OH

(CH 3) 3 c 4 CH 3 CH 3 C (CH 3) 3

O O

(CH 2) 6OC C (CH 2) 6

C -O - (CH 2) 6

0 t

CH 3 C (CH 3) 3

  OH (Compound No. 36); IR absorption of the carbonyl band at 1722 cm-r Composition: calc 75.9% C, 8.9% H, found 75.3% C, 9.3% H.

EXAMPLE 37

* In a round-bottomed flask with a column of

  distillation, 16.5 g (70 mmol) of 4- (3-

  tert-butyl-5-methyl-4-hydroxyphenyl) butanol, 18.05 g (91 mmol) of methyl ester of 10-undecenoic acid

  and 80 mg (1.4 mmol) of dibutyltin oxide.

  The mixture is heated to 180 ° C., while distilling off the methanol After 2 hours, the pressure is lowered to 400 torr and then maintained.

  the temperature at 180 C for an additional 2 hours.

  The excess methyl ester of the undecenoic acid is then distilled off and the crude product obtained (brown oil) is purified by chromatography.

  (If O 2, hexane / ethyl acetate = 9/1).

  23.15 g (82%) of a product corresponding to the formula: ## STR2 ## (C H) 8 C>% are obtained.

OY _ CH 2

O

  Composition and IR data: see table 6.

EXAMPLES 38 TO 42

  Compounds Nos. 38 to 42 are prepared in a manner analogous to the process described in Example 1. The data relating to the composition and IR of compounds Nos. 38 to 40 are shown in Table 6, the corresponding data.

  compounds 40 and 41 in Table 7.

TABLE 6

  Composition and IR data for compounds 37 to 40 OH Compound type:

(CH 3) 3 C.

O

I O I

  (CH 2) rO -C A COMP N COMPOSITION IR: 1 / n O C%: H%: C = O calc found calc found lcn 71 l

  37 4 - (CH 2) 8-CH = CH 2 77.56 77.59 10.52 10.58 1719/1735

  38 4 -C (CH 3) = CH 274.96 74.95 9.27 9.48 1705

  39 6 -CH = CH 2 75.43 75.20 9.50 9.53 1712/1725

  6 -C (CH 3) = CH 275.86 75.83 9.70 10.16 1705/1718

CH 3

TABLE 7

  Composition and IR data for compounds 41 to 42 OH

(CH 3) 3 C C (CH 3) 3

Type of compound:

(CH 2) -O -C-A

  COMP N A IR COMPOSITION: 1/1 n C%: H%: C = O calc found calc found lcm-1 l

  41 6 -CH = CH 2 76.61 76.44 10.06 10.08 1725

  42 6 -C (CH 3) = CH 276.96 76.85 10.23 10.16 1719

EXAMPLES 43 TO 45

  Compound No. 43 is prepared by the method described in Example 1. Compound No. 44 is prepared by the method described in Example No. 37; Compound No. 45 is prepared by the method described in Example No. 23 Data concerning the composition and IR of the compounds

  Nos. 43 to 45 are shown in Table 8.

TABLE 8 Composition and IR data for compounds 43 to 45 OH (CH)

  3) 3 c CH 3 CH 3 C (CH 3) 3 Compound type: 1 O II il (CH 2) -OCACO - (CH 2) n Comp NA IR COMPOSITION: 1/1 n C%: H%: C = O calc found calc found lcm-1 l

  43 4 -CH 2-CH 2 73.61 73.14 9.08 9.21 1722

  44 4 (CH 2) 2-O (CH 2) 2 72.21 71.93 9.09 9.20 1728

6 72.25 72.41 8.49 8.53 1717

S S%: calc 4.82 found 4.69

EXAMPLE 46

  a) Esterification of the mixture of dicarboxylic acids with methanol To a solution of 52 g (0.4 mol) of mixture of dicarboxylic acids (BASF manufacturer, consisting of 25-35% succinic acid, 37-47% d glutaric acid and 25-30% of adipic acid) in 450 ml of methanol, 22 ml (0.41 mol) of concentrated sulfuric acid are added dropwise at 10 ° C. The solution obtained is maintained at room temperature. After cooling to 20-25 ° C., the mixture is neutralized with g of potassium carbonate, poured into water and extracted with ethyl acetate. 23 g (36%) of the desired ester mixture

  in the form of a slightly yellowish oil.

  Gas chromatographic analysis of the mixture of compounds corresponding to the formula:

H 3 C-OCO- (CH 2) X-COO-CH 3

  x = 23 mole% x = 34 mole% x = 4 33 mole% b) Preparation of compound 46 In a round-bottomed flask equipped with a column of

  distillation, 30.7 g (130 mmol) of 4- (3-

  tert-butyl-5-methyl-4-hydroxyphenyl) butanol, 8.01 g (50 mmol) of the diester mixture described in a) and 490 mg

  (2 mmol) dibutyltin oxide.

  The mixture is heated to 180 ° C. while distilling off the methanol.

   C for another 15 hours After cooling

  at 20-25 ° C., the crude mixture is purified by chromatography.

  tography (SiO 2, hexane / ethyl acetate 40: 1 -> 19: 1 -> 9: 1). 17.1 g (60%) of compound 46 are obtained under the

form of a yellow oil.

  Composition and IR data: see

table 9.

EXAMPLES 47 TO 51

  The preparation of compounds 47 and 48 was carried out using phenolic alcohols

  corresponding by the method described in Example 46.

  For the preparation of compounds 49, 50 and 51,

  first synthesized from Poly-THF-

  Dipropionate 350 (manufacturer: Bayer AG, Leverkusen), the corresponding methyl ester by the method described in Example 46 The resulting high molecular weight dicarboxylic acid methyl ester is then converted to the end products indicated using alcohols. phenolic

  method described in Example 46.

  The data concerning the composition and the IR of the

  Compounds Nos. 46 to 51 are shown in Table 9.

(See Table 9 on the next page)

TABLE 9

  Composition and IR data for compounds 46 to 51 Compound type (diester and oligomer mixtures) Comp R 1 NA IR COMPOSITION: 1 / n C%: H%: C = O calc found calc found lcm 1 in which 46 Me 4 x = 2 20-25% 73.91 * 73.79 9.22 9.37 1719 4 B (CH 2)> xx = 3 40-43% 47t-Bu4 x = 4 34-38 % 75.43 * 75.05 9, 88 * 9.98 1735 48 Me 6 21% x = 2; 42% x = 3; 37% x = 474.96 * 74.919, 68 * 9.81 1720 49 Me 4 7 F: 7993 OC 70.26 69.92 9.61 9.78 1735 t-Bu 4 (CH 220 - + (CH 2) 4-Oly (CH 2) 271.6771.92 9.95 10.21 1737 51 Me 6 y = 2.6 71.70 71.19 9.96 9.97 1736 Me = methyl; t-Bu = tert- butyl * Composition calculated for x = 3

EXAMPLE 52

  (a) Preparation of the methyl ester of nitrilotriacetic acid To a suspension of 100 g (0.52 mol) of nitrilotriacetic acid in 200 ml of methanol is added dropwise, at about 10 ° C., 8 ml (137.7 g)

  (1.4 mole) concentrated sulfuric acid.

  The mixture is kept at reflux temperature for 22 hours. After cooling to room temperature, the mixture is neutralized by cautiously adding 150 g of potassium carbonate.

  poured on water and extracted with ethyl acetate.

  Evaporation of the solvent and drying of the residue under vacuum provided 57 g (47%) of the nitrilotriacetic acid methyl ester as a colorless oil. IR (K Br crystal film): Carbonyl absorption at 1751 cm -1 Composition: Calculated 46.35% C 6, 48% H 6.0% N Found 46.47% C 6.53 % H 6,14% N b) Preparation of the compound n 52 1.76 g (7.5 mmol) of methyl ester of the acid are introduced into a round bottom flask equipped with a distillation column. nitrilotriacetic, 7 g

  (29.4 mmol) 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., while distilling off the methanol After 3 hours, the pressure is lowered to 400 torr and the mixture is maintained at room temperature. temperature at 180 C for 2 hours

additional.

  The excess of 4- (3-tert-butyl-5-

  methyl-4-hydroxyphenyl) -butanol by distillation (150 ° C. / 0.4 Pa) and the crude product obtained (SiO 2, hexane / ethyl acetate 9: 1) is purified by chromatography.

3: 1).

  5.6 g (88%) of a product corresponding to the formula

H 3 CCH 3 H

CH 3 CH 3

(CH 2) 4

o CH 2 N y IH

  Composition and IR data: see table 10.

  EXAMPLES 53 TO 53 The preparation of compounds 53 and 55 is carried out by the method described in Example 52. The composition and IR data of the compounds are collected in

table 10.

TABLE 10

Type of compound:

CH CH 3 H 1

CH (CH 2) n

O-F CH 2-

  O -N Comp R 1 NF IR COMPOSITION: 1/1 n C: H%: S%: C = O calc found calc found calc found lcm 1 l 52 Me 4 72.39 72.39 8.93 8, 83 1 , 66 1.48 1738 53 t-Bu 4 74.11 73.42 9.64 9.68 1.44 1.23 1747 54 Me 6 73.59 72.98 9.43 9.67 1.51 1, 31 1739 t-Bu 6 75.03 74.18 10.02 10.28 1.33 1.33 1748

EXAMPLES 56 TO 60

  The preparation of compounds 56 to 60 is carried out by the method described in Example 36. The composition and IR data of the compounds are collected in

table 11.

(See table 11 next page)

TABLE 11

  Compound type: OH R 1 A jz Comp R 1 A z F IR COMPOSITION: 1 / X n C%: H%: C = O calc found calc found lcmr-1 l 56 t-Bu 3 77.05 77.28 9,56 9,53 1727 57 Me 3 62-65 75.91 75, 95 8.92 8.92 1728 58 t-Bu 3 95-97 77.05 76.09 9.56 9, 67 1729 N 59 Me 4 75.57 74.95 8.94 9.65 1725 t-Bu 4 76.77 71.14 9.59 8.91 1730

EXAMPLE 61

  Preparation of 4- (3,5-dicyclohexyl-4-hydroxy)

  phenyl) -hexanol In a sulfonation flask, 258 g (1 mol) are melted

  of 2,6-dicyclohexylphenol, 591 g (5 moles) of 1,6-hexane

  diol and heated for 10 hours at 238 C with 36 g (0.64 mole) of potassium hydroxide The mixture is then slightly acidified to 80 C with a solution

  The phases are separated off, the mineral phase is washed with toluene and the combined organic phases are concentrated on a rotary evaporator. The excess 1,6-hexanediol and 2,6-dicyclohexylphenol are distilled off. not reacting.

  Crystallization of the residue on a definite boiling gasoline (80-110 ° C.) gives 163 g (45%) of a product corresponding to the following formula:

F = 96 C

Composition: calculated found

(CH 2) 6

  OH, 39% C 10.68% H 78.62% C 10.62% H

EXAMPLE 62

  32.3 g (90 mmoles) of 4- (3,5-dicyclo

  hexyl-4-hydroxyphenyl) -hexanol using 9.2 g (50 mmol) of adipic acid dichloride, by the method described in Example 1c, in 18.7 g (47%) of a product corresponding to to the formula: OH

(CH 2) 6

o C (CH 2) 4 c it i

O O

i

  The compound is obtained in the form of a viscous oil.

  IR (K Br crystal film): 1736, 1717 cm-1 (C = O) Composition: calculated 77.76% C 10.29% H Found 77.62% C 10.05% H

EXAMPLES OF APPLICATION

  EXAMPLE 63 Stabilization of polypropylene 100 parts of polypropylene powder containing 0.1% of calcium stearate are mixed with 0.3% of distearyl thiodipropionate (DSTDP) and 0.1% of the stabilizer according to the invention indicated. in Example 12, and then kneaded for 10 minutes at 200 ° C. in a

Brabender Plastograph.

  The mass thus obtained is compressed in a press having a surface temperature of 260 ° C. to obtain a plate 1 mm thick, in which strips 1 cm wide and 10 cm long are cut for comparison. Another sample without stabilizers is prepared. Several of these strips of each plate are suspended in an air circulation oven heated to C or 149 ° C., and examined at regular intervals. The oxidative decomposition of these bands is manifested by one of yellow color starting in a circle shape A measure for the stability of the sample

  is the duration in days until decomposition.

(See table 12 next page)

TABLE 12

  Duration (in days) until the decomposition of the samples containing the combination of stabilizers 0.3% of DSTDP + 0.1% of the compound of the invention or no stabilizer Number of days of aging Stabilizers the oven up to decomposing

at 135 C to 149 C

  None 1 <1 DSTDP + compound n 8 126 50 DSTDP + compound n 13 115 40 DSTDP + compound n 17 156 65 DSTDP + compound n 20 162 60 DSTDP + compound n 21 175 38 DSTDP + compound n 22 247 57 DSTDP + compound n 23 245 85 DSTDP + Compound No. 24 140 43 DSTDP + Compound No. 25 121 24 DSTDP + Compound No. 26 151 33 DSTDP + Compound No. 28 147 47 DSTDP + Compound No. 29 145 49 DSTDP + Compound No. 30 194 50 DSTDP + Compound No. 35 148 50 DSTDP + Compound No. 36 190 71 DSTDP + Compound No. 52 158 55 DSTDP + Compound No. 53 158 48 DSTDP + Compound No. 54 161 55 DSTDP + Compound No. 55 150 43 DSTDP + Compound No. 56 170 52 DSTDP + Compound No. 57 193 70 DSTDP + Compound No. 58 173 52 DSTDP + Compound No. 59 163 63 DSTDP + Compound No. 60 159 48

  EXAMPLE 64 Stabilization of an Acrylic Terpolymer

  nitrile-butadiene-styrene (ABS) The stabilizers listed in Table 13 are

  dissolved in 40 ml of a mixture of hexane and isopropanol.

  The solution is poured with vigorous stirring in a dispersion of 100 g of ABS in 600 ml of water, after which the solution is completely absorbed by the ABS in about one minute. The polymer powder containing the stabilizers is then filtered and vacuum drying at 40 OC for

hours.

  The other stages of processing are also carried out for comparison with a

sample without stabilizers.

  To the dried powder is added as pigment 2% of

  titanium dioxide and as a lubricant 1% ethylene-bis-

  stearamide The mixture is then mixed over a period of

  4 minutes on a two-cylinder mill at 180 OC.

  From the kneaded web, a plate 0.8 mm thick was pressed at 175 ° C., in which 45 × 17 mm 2 specimens were cut. The effectiveness of the added stabilizers was tested by aging. in a circulating air oven at 180 ° C. As a criterion, the appearance of color is used after a period of 45 minutes. The intensity of the color is determined by ASTM D 1925 (degree of yellow) The results of the tests are shown in Table 13. The highest figures correspond to the most intense yellow color. The tests show that the yellow color is effectively repressed by

  the compounds according to the invention.

(See table 13 next page)

TABLE 13

  Degree of yolk after 45 minutes of aging in the oven of samples containing no stabilizers, containing 0.5% dilauryl thiodipropionate (DLTDP) and 0.5% DLTDP + 0.25% of the compound according to Stabilizing agents Degree of yolk after 45 min at 180 C None DLTDP 75 DLTDP + compound n 1 26 DLTDP + compound n 7 25 DLTDP + compound n 8 26 DLTDP + compound n 12 34 DLTDP + compound n 13 39 DLTDP + Compound No. 15 DLTDP + Compound No. 16 34 DLTDP + Compound No. 17 26 DLTDP + Compound No. 19 31 DLTDP + Compound No. 20 26 DLTDP + Compound No. 21 33 DLTDP + Compound No. 22 21 DLTDP + Compound No. 23 29 DLTDP + compound n 24 32 DLTDP + compound n 25 41 DLTDP + compound n 26 28 DLTDP + compound n 28 30 DLTDP + compound n 29 32 DLTDP + compound n 31 29 DLTDP + compound n 32 27 DLTDP + compound n 33 32 DLTDP + compound n 34 DLTDP + Compound No. 39 36 DLTDP + Compound No. 40 26 DLTDP + Compound No. 42 32 EXAMPLE 65 Stabilization of Latex X -SBR (carboxylated SBR latex) 0.25 parts by weight of the compounds in accordance with the invention indicated in Table 14 are dissolved in a small amount of methanol and they are stirred into

  parts by weight of latex X-SBR (styrene copolymer)

  butadiene) Petri dishes are then fed with an exactly defined amount of latex and dried in an 80 OC drier. Transparent films having a layer thickness of about 0.2 mm are obtained.

  comparison, a sample without stabilizers is prepared.

  The effectiveness of the indicated stabilizers is tested by thermal aging in an air-circulating oven at 135 ° C. At the end of the time intervals indicated in Table 14, the color of the samples is determined according to ASTM D 1925. -70 (yellow degree) The test results are shown in Table 14. The highest numbers correspond to the most intense yellow color. The tests show that the yellow color is repressed in a very

  effective by the compounds according to the invention.

TABLE 14

  Degree of yellowness at the end of the indicated aging time at 135 ° C Degree of yellowness Stabilizing after aging time of 4 h 12 h 24 h 40 h None 92 * * * 0.25% of compound NO 31 46 52 64 75 0.25% of compound NO 32 40 46 58 69 * not measurable (black sample)

Claims (16)

  Compound of formula I: OH (I) Rl 'R 1 (CH 2) -O C A   wherein N is an integer from 4 to 8 and m is an integer from 1 to 4; A, in the case where m is 1, represents a C 1 -C 25 alkyl group, which is unsubstituted or substituted by a C 5 -C 8 cycloalkyl group; or it represents a C 2 -C 25 alkyl group, which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of -S-, -O and / or -NR 2 groups; or in the case where m is 1, A is C 5 -C 8 cycloalkyl which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; C 6 -C 8 cycloalkenyl which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; a phenyl group, which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; a naphthyl group, which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; a biphenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; or a C 2 -C 25 alkenyl group; a C 6 -C 20 bicycloalkenyl group; a C 7 -C 12 phenylalkyl group; a C 8 -C 12 phenylalkenyl group; a C1-C16 naphthylalkyl group; a C 12 -C 16 naphthylalkenyl group; a C 13 -C 18 biphenylalkyl group; a C 14 -C 18 biphenylalkenyl group; or a group of formula II: R 4 -CH 2 CH 2 OH R 3 (II);   R 3 in the case of 0 is 2, A is a direct bond, C 1 -C 12 alkylene, C 2 -C 12 alkenylene, C 5 -C 8 cycloalkylene, which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; a C 6 -C 8 cycloalkenylene group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; a C 6 -C 20 bicycloalkenylene group, a phenylene group, a naphthylene group, a divalent heterocyclic radical chosen from furan, thiophene or pyrrole, which is saturated on the nitrogen atom with hydrogen atoms or the substituent -R 2, or A, in the case where om is 2, denotes a C 2 -C 36 alkylene group interrupted by a C 5 -C 8 cycloalkylene group or phenylene or at least one of the -S groups -, -OO or -NR 2; A, in the case where om is equal to 3, denotes a group (C 1 -C 8 alkane) triyl; a group (C 2 -C 8 alkene) triyl; a benzenetriyl group; a G roup naphthalenetriyl, a trivalent group meeting the R 6-   formula -R 5 -N-R 7 or a group (C 2 -C 18 alkane) triyl, which is interrupted by at least one of -S-, -O or -NR 2-;   A, in the case where m is 4, denotes a benzene radical; naphthyl; tetrahydrofuryl or cyclohexyl having 4 free valencies; R 1 and R 1 T 'independently of one another are C 1 -C 10 alkyl or C 5 -C 8 cycloalkyl; R 2 represents H or a C 1 -C 4 alkyl group; R 3 and R 4 denote independently of one another a C 1 -C 4 alkyl group; and R 5, R 6 and R 7 independently of one another a C 1 -C 3 alkylene group.   A compound of formula I according to claim 1, wherein R 1 'is C 3 -C 24 secondary or tertiary alkyl or C 5 -C 5 cycloalkyl; and R 1 is C 1 -C 10 alkyl or cycloalkyl C 5-C 8   3 Compound corresponding to formula I according to   claim 1, wherein R 1 'denotes a group tert-   butyl and R 1 denotes a methyl group.   4 Compound corresponding to the formula Ia OH (CH 3) 3 C R 1 O I (CH 2) -Oc C A N T   wherein N is an integer from 4 to 8 and m is an integer from 1 to 3; A, in the case where om is 1, represents a C 1 -C 25 alkyl group, which is unsubstituted or substituted by a C 5 -C 8 cycloalkyl group, or is a C 2 -C 4 alkyl group; C 25, which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of -S-, -O and / or -NR 2 groups; or A, when m is 1, denotes a C 5 -C 8 cycloalkyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; a C 6 -C 8 cycloalkenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl or C 2 -C 12 alkenyl group; phenyl, which is unsubstituted or substituted by C 1 -C 12 alkyl or C 2 -C 12 alkenyl; naphthyl, which is unsubstituted or substituted by 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; C 6 -C 20 bicycloalkenyl; C 7 -C 12 phenylalkyl; C 7 -C 12 phenylalkenyl; C1-C16 naphthylalkyl; C 11 -C 16 naphthylalkenyl; C 13 -C 18 biphenylalkyl; C13-C18 biphenylalkenyl OR a group of formula II: R loR OH -CH 2 CH 2   A, when m is 2, denotes a direct bond, C 1 -C 12 alkylene, C 2 -C 12 alkenylene, C 8 -C 8 cycloalkylene which is unsubstituted or substituted by C 1 -C 8 alkyl. 1-C 12 or C 2 -C 12 alkenyl, C 6 -C 8 cycloalkenylene, which is unsubstituted or   substituted with C1-C12 alkyl or C 2- alkenyl   C 12, C 6 -C 20 bicycloalkenylene; phenylene, naphthylene, or C 2 -C 18 alkylene interrupted by C 5 -C 8 cycloalkylene or phenylene or by at least one of -S-, -O or -NR 2; A, when m is 3, denotes a group (C 1 -C 8 alkane) triyl, (C 2 -C 8 alkene) triyl, benzenetriyl, naphthalenetriyl; a trivalent group corresponding to the R 6 formula -R 5 -N-R 7 or a group (C 2 -C 18 alkane) triyl, which is interrupted by at least one of -S-, -O or -NR 2; R 1 represents a methyl or tert-butyl group; R 2 represents an E atom or a C 1 -C 4 alkyl group; R 3 and R 4 denote independently of one another a C 1 -C 4 alkyl group; and R 5, R 6 and R 7 independently of one another a C 1 -C 3 alkylene group.   A compound of formula I according to claim 1, wherein A, in the case where om is 1, represents a C 2 -C 25 alkyl group which is unsubstituted or substituted by a C 5 -C 8 cycloalkyl group or it is a C 2 -C 25 alkyl group which is interrupted by a C 5 -C 8 cycloalkyl group or by one or more of the groups -S-, -O and / or -NR 2; or A, when m is 1, means a C 5 -C 8 cycloalkyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; a C 6 -C 8 cycloalkenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; a phenyl group which is unsubstituted or substituted by   a C1-C12 alkyl group; or a C 2- alkenyl group   C 25; a C 7 -C 12 phenylalkyl group; or a group of formula II: R -CH 2 CH 2 / OH R 3 (II),   RB A, when m is 2, denotes a direct bond, a C 1 -C 12 alkylene group, C 2 -C 12 alkenylene, C 5 -C 8 cycloalkylene, which is unsubstituted or substituted by a group C 1 -C 12 alkyl, C 6 -C 8 cycloalkenylene which is unsubstituted or substituted by C 1 -C 12 alkyl; a phenylene group; a divalent heterocyclic radical selected from furan, thiophene or pyrrole, which is saturated on the nitrogen atom with hydrogen atoms or the substituent -R 2-; or A, when m is 2, denotes a C 2 -C 18 alkylene group interrupted by a cycloalkylene group in   C 5 -C 8 or phenylene, or by at least one of the groups -S-, -O-   or -NR 2; and A, when m is 3, denotes a group (C 1 -C 8 alkane) triyl, (C 2 -C 8) alkene triyl, benzenetriyl; a trivalent R 6 -group having the formula -R 5 -N-R 7; or a C 2 -C 18 alkane triyl group which is interrupted by at least one of -S-, -O or -NR 2; and A, when m is 4, denotes a benzene radical or   cyclohexyl having 4 free valences.   6 Compound corresponding to formula I according to   claim 1, wherein R 1 'denotes a group tert-   butyl or cyclohexyl and R 1 denotes a methyl, tert-butyl or cyclohexyl group; n is a number from 4 to 6; and A, when m is 1, is C 6 -C 18 alkyl or C 2 -C 12 alkenyl; A, when m is 2, represents a direct bond; a C 1 -C 12 alkylene group; a phenylene group; or a C 2 -C 36 alkylene group interrupted with 1 to 5 oxygen or sulfur atoms; A, when m is 3, denotes a benzenetriyl group CH 2-   or a trivalent group having the formula -CH 2 -N-CH 2; and A, when m is 4, denotes a benzene radical having 4 free valences.   Compound of formula I according to claim 1, wherein N is a whole number between 5 and 8.   Compound of formula I according to claim 1, wherein N is a whole number between 6 and 8.   9 Compound of formula I according to   claim 6 wherein m is 1 or 2.   A compound of formula I as claimed in claim 9, having the formula: HO OH CH 3 t C (CH 3) 3 CH 3 <C (CH 3) 3 (CH 2) 6 A CC- (CH 2) 6 (CH 2) A C 0- (H)   wherein A is - (C 2) (CH 2) j; - (C 2) k-S (C 2) k -; / s or - (CH 2) 2 -O-1 (CH 2) 2 -O-1 - (CH 2) 2; j is 0 or an integer of 1 to 4; and k denotes a integer between 1 and 3. 11 One of the compounds a) to 1)   a) 6- (3-tert-butyl-4-hydroxy-5- stearate) methylphenyl) hexyl;   b) 6- (3,5-di-tert-butyl-4-hydroxy) stearate phenyl) hexyl;   c) succinate bis-1 6- (3-tert-butyl-4-hydroxy-5- methylphenyl) -hexylel;   d) bis-1 6- (3-tert-butyl-4-hydroxy-5-) adipate methylphenyl) -hexylel;   e) the bis-1 6- (3-tert-butyl-4-hydroxy-5- methylphenyl) -hexylel;   f) bis-1-6- (3-tert-butyl-4-hydroxy-5-) isophthalate methylphenyl) -hexylel;   g) bis-1 6- (3,5-di-tert-butyl) -4-isophthalate hydroxyphenyl) -hexylel;   h) tris-1-6- (3-tert-butyl-4-hydroxy-trimellitate) 5-methylphenyl) -hexylel;   j) Tris-1-6- (3,5-di-tert-butyl-4- trimellitate hydroxyphenyl) -hexylel;   k) Tris-1 6- (3-tert-butyl-4-hydroxy-5-) trimesinate methylphenyl) -hexylel;   1) Tris-1 6- (3,5-di-tert-butyl) -4-trimesinate   hydroxyphenyl) -hexylel according to claim 1. 12 Compound of formula III ## STR2 ## (CH 2) OH   in which G 1 and G 1 'are, independently of each other, a C 1 -C 24 alkyl or C 5 -C 8 cycloalkyl group, the tert-butyl meaning being excluded for G 1, and n   is an integer between 4 and 8.   The compound of claim 12 wherein Gl 'is a tert-butyl or cyclohexyl group and G 1 is a methyl or cyclohexyl group.   Composition containing an organic material sensitive to thermal, oxidative and / or actinic degradation and at least one compound of formula I according to claim 1.   The composition of claim 14, wherein the organic material is a synthetic organic polymer or a mixture of these polymers.   The composition of claim 15, wherein the synthetic organic polymer is a polyolefin or a styrene copolymer.   Use of compounds of formula I according to claim 1 for the stabilization of an organic material against thermal degradation, oxidizing and / or actinic.   Use of compounds of formula I according to claim 17 as antioxidants in   synthetic organic polymers.   Process for the stabilization of an organic material with respect to thermal, oxidative and / or actinic degradation, characterized in that at least one compound of formula I is added to this material. organic material sensitive to thermal, oxidative and / or actinic degradation and at least one compound corresponding to the formula ## STR1 ## wherein N is an integer of between 4 and 8; and RI and R 1 'independently of one another represent   C 1 -C 24 alkyl or C 5 -C 8 cycloalkyl.   Use of compounds of formula IV according to claim 20 for the stabilization of an organic material against thermal degradation, oxidizing and / or actinic.