BE1006547A5 - Acid esters of carboxylic hydroxyphenylalcanols as stabilizers. - Google Patents

Abstract

New compounds corresponding to formula I: (see fig) 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 represent, independently of one another, a C1-C10 alkyl or C1-C8 cycloalkyl group.

Description

       

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   Carboxylic acid esters of hydroxyphenylalkanols as stabilizers.



   The present invention relates to new 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 new compounds as stabilizers as well as new (o- (3,5-dialkyl-4-hydroxyphenyl) -alkanols.



   The use [of esters] of CO-hydroxyphenyl-a-carboxylic acid esters as stabilizers for organic materials is known.



   A series of publications deals with the corresponding reverse 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. il 106614c, Chem. Abstr. 106 156001u, US-A-4,910. 286, US-A-4.311. 637, US-A-4.104. 252 and US-A-3,919. 097 describe esters of 3- (3, 5-di-tert-butyl-4hydroxyphenyl) -alkan-1-ols, 3- (3-tert-butyl-5-methyl-4-) carboxylic acids
 EMI1.1
 hydroxyphenyl) -alkan-1-ols and various 4- (3,5-dialkyl-4hydroxyphenyl) -alkan-1-ols, as well as their use as stabilizers for polymers.



   We have now found a few esters of new carboxylic acids of ar- (3,5-dialkyl-4-hydroxyphenyl) alkanols which have particularly good stabilizing properties.



   One of the objectives of the present invention is therefore compounds corresponding to formula I:
 EMI1.2
 in which n denotes an integer between 4 and 8 and m denotes an integer between 1 and 4;

  <Desc / Clms Page number 2>

 A, in the case where m is equal to 1, represents a C1-C2 alkyl group. which is unsubstituted or substituted or by a C 1 -C 5 cycloalkyl group; or it represents a C2-C25 alkyl group which is interrupted by a Cg-Cg cycloalkyl group or by one or more of the groups -S-, -O- and / or -NR2-;

   or, in the case where m is equal to 1, A denotes a Cs-C8 cycloalkyl group which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; a C6-C8 cycloalkenyl group which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; phenyl, which is unsubstituted or substituted by a C1-C12 alkyl or Cs-Ciz alkenyl group; naphthyl, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; biphenyl, which is unsubstituted or substituted by a C1-C2 alkyl or C2-C12 alkenyl group; or a C2-C25 alkenyl group; C 8 -C 10 bicycloalkenyl; C7-C12 phenylalkyl;

   Cs-Cis phenylalkenyl; Cn-Cig naphthylalkyl; Ciz-Cig naphthylalkenyl; C13-C18 biphenylalkyl; C14-C18 biphenylalkenyl; or a group corresponding to formula II:
 EMI2.1
 in the case where m is equal to 2, A denotes a direct bond; a C1-C12 alkylene group; C2-C12 alkenylene; C1-C6 cycloalkylene which is unsubstituted or substituted by C1-C12 alkyl or C2-C12 alkenyl; Cg-Cg cycloalkenylene, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; C6-C10 bicycloalkenylene; phenylene; naphthylene;

   a divalent heterocyclic radical chosen from furan, thiophene or pyrrole, which is saturated on the nitrogen atom with hydrogen atoms or the substituent -R2-; or A, if m is equal

  <Desc / Clms Page number 3>

 to 2, denotes a C2-C36 alkylene group interrupted by a Cs-C8 or phenylene cycloalkylene group or by at least one of the groups -S-, -O- or -NR2-; A, in the case where m is
 EMI3.1
 equal to 3, denotes a C1-C6 alkanetriyl group; Cs-C6 alkenetriyl / benzotriyl; naphthalenetriyl; a
 EMI3.2
 R6 1 trivalent group corresponding to the formula-R-N-R-or a
 EMI3.3
 Cz-Cig alkanetriyl group which is interrupted by at least one of the groups -S-, -0- or -NR2-;

   A, in the case where m is equal to 4, denotes a benzene radical; naphthyl; tetrahydrofuryl or cyclohexyl having 4 free valences; Rl and Ri're independently of one another represent a C1-C24 alkyl or a Cg-Cg cycloalkyl group; R2 represents an H atom or a C1-C4 alkyl group; R3 and R4 independently of one another denote a C1-C4 alkyl group; and R, R6 and R7 independently of one another represent a C1-Os alkylene group.



   When they represent a C1-C24 alkyl or Cg-Cg cycloalkyl group, RI and Ru 'denote independently of each other for example a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl group , nonyle, décyle, cyclopentényle, cyclohexyle, cycloheptyle ou cyclooctyle.



     It is preferably a secondary or tertiary C3-C24 alkyl group, for example a 2-butyl (sec-butyl), tert-butyl, 2-pentyl, 2-hexyl or 3-hexyl group, or else R1 'is a C6-C8 cycloalkyl group, for example a cyclohexyl group and R1 C1-C10 alkyl or a Cs-C6 cycloalkyl.



   It is particularly preferred that Ru 'denotes a secondary or tertiary Cs-Cis alkyl group or Cs-Cg cycloalkyl, for example an isopropyl, sec-butyl, tert-butyl or cyclohexyl group, and RI a Cs-Cg alkyl or a Cs-Cg cycloalkyl or else a methyl group. Particularly preferred are compounds corresponding to formula I in which RI denotes a

  <Desc / Clms Page number 4>

 methyl, tert-butyl or cyclohexyl group, in particular a methyl group, and that Ru 'denotes a tert-butyl or cyclohexyl group, in particular a tert-butyl group.



     R2, R3 and R4, when they denote a C1-C4 alkyl group, represent a methyl, ethyl, 1-propyl (n-propyl), 2-propyl (isopropyl), 1-butyl (n-butyl) group, 2-butyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1dimethylethyl (tert-butyl), a methyl or tert-butyl group is preferred.



   When they are a C1-C3 alkylene group, R, R6 and R7 denote a methylene group, 1, 1- or 1,2-ethylene or 1,1-, 1,2-, 2, 2- or 1, 3-propylene. A methylene group is preferred.



   If A represents a C1-C25 alkyl group, it is a branched or unbranched radical, for example a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, 2-ethylbutyl,
 EMI4.1
 n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3methylheptyl, n-octyl, 2-ethylhexyl, 1,1, 3trimethylhexyl, 1, 1,3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1.1, 3.3, 5.5hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl or pentacosyl; an unbranched alkyl group is preferred, and
 EMI4.2
 more preferably an unbranched C6-Cis alkyl group.



  A, when it denotes a C 1 -C 6 alkyl group substituted by a C 5 -C 6 cycloalkyl group, is for example a cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclohexylethyl, 2-cyclohexyl-n-propyl, 3-cyclohexyl group n-propyl, 4-cyclohexyl-n-butyl.



   A, when it denotes a C-Czs alkyl group interrupted by a Cs-Cs cycloalkyl group or by one or more of the groups S, O, and / or NR2, represents one of the alkyl radicals described below above except

  <Desc / Clms Page number 5>

 methyl radical, in the chain of which a cyclopentylene or pentylidene, cyclohexylene or hexylidene, cyclooctylene or-heptylidene, cyclooctylene or-octylidene group, or in one or more places the groups mentioned above with heteroatoms have been introduced at one place.

   A therefore answers for example the formulas
 EMI5.1
 
A, when it denotes a Cs-Cg cycloalkyl or Cg-Cg cycloalkenyl group which is unsubstituted or substituted by a C1-C12 alkyl or alkenyl group
 EMI5.2
 Cz-C1Z, may for example be a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1- or 4-cyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, 2-cyclohexenyl, 3-cycloheptenyl, cyclooctatenyl, cyclooctatenyl group -2-enyl. The cyclohexyl and cyclohexenyl groups are preferred, in particular the cyclohexyl group.



   A, when it denotes a phenyl, naphthyl or biphenyl group substituted by a C1-C12 alkyl group or ¯CZ-C1Z alkenyl, denotes inter alia a methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, vinylphenyl, diethylphenyl, isopropylphenyl, tertiary group -butylphenyl, di-tert-butylphenyl, methyl-di-t-butylphenyl, 1, 1,3, 3-tetramethylbutylphenyl and 1, 1,3, 3,5, 5-hexamethylhexylphenyl, dodecenylphenyl, l-methylnaphthyl, 2-methylnaphthyl , 1-ethylnaphthyl, 2-propyl-biphenyl-4-yl, 4- (1-hex-3-enyl) -biphenyl-8-yl.



  Preferred here is a phenyl group which is optionally substituted by one to three, for example one to two, in particular a C1-C4 alkyl group, mainly a methyl group.



   When it denotes a C2-C25 alkenyl group, A is for example a vinyl, propenyl, isopropenyl group,

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 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl-n- octadec-2-enyl, n-octadec-4-enyl.



   When it denotes a C7-Cl2 phenylalkyl group, a C7-Cl2 phenylalkenyl group, a C1-Cl6 naphthylalkyl group, a C11-Cl6 naphthylalkenyl group, a C1-3-C8 biphenylalkyl group or a C13- biphenylalkenyl group ClS, A represents a C1-C6 alkyl or C1-C6 alkenyl group which is substituted by a phenyl, naphthyl or biphenyl group such as benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, a, a-dimethylbenzyl,
 EMI6.1
 2-phenylethenyl, 1-phenylprop-2-enyl, 6-phenylhexyl, l-naphthylmethyl, 2-naphtylmethyl, 1-naphtyleth-l-yl, 2- (4-biphenylyl) -prop-2-yle, l- (4 -biphenylyl) -pent-3-en-l- yle.



   When it denotes a Cg-Cio bicycloalkenyl or Cg-Cio bicycloalkenylene group A is a monovalent or divalent Cg-Cio unsaturated radical which, when it is a monovalent radical, is for example a bicyclo- (2, 2, 1) -hepta-5-en-2-yl, and when it is a divalent radical, can respond for example to the formulas
 EMI6.2
 
The divalent (for m = 2), trivalent (for m = 3) and tetravalent (for m = 4) radicals are derived from the monovalent radicals mentioned above.

   A divalent radical is distinguished from the corresponding monovalent radical in that it contains, in place of a hydrogen atom, an open bond; a trivalent radical is distinguished from the corresponding monovalent radical in that it contains, in place of two hydrogen atoms, two open bonds; a tetravalent radical differs from the corresponding monovalent radical in that it contains, instead of three

  <Desc / Clms Page number 7>

 hydrogen atoms, three open bonds.

   Thus A, in the context of the indicated meanings, can when it is for example a divalent radical, represent
 EMI7.1
 also a methylene, ethylene, -CH2-C (CH3) 2-CH2- 'prop-2-en-ylidene, propylene- (1,3), butylene- (1,4), pentylene- (1,5) radical ,
 EMI7.2
 hexylene- (1,6), o-, m-or p-phenylene, '2' \ "2 ', - CH-CH- yHs-CH - CH-SH-ou-CH-O-CH-. s 'he
 EMI7.3
 represents a trivalent radical, this will for example
 EMI7.4
 
 EMI7.5
 represents a tetravalent radical, it will be for example.

   1
 EMI7.6
 
 EMI7.7
 The new esters corresponding to formula I can be prepared by standard esterification or transesterification methods from CO-hydroxyphenylalkanols corresponding to formula IV
 EMI7.8
 and organic carboxylic acids corresponding to formula V
 EMI7.9
 or derivatives of these carboxylic acids, for example by the methods described in Tetrahedron 36, 2409 (1980). The symbols Ri, R1 ', A, n and m of the formulas IV and V have the meanings indicated above for the formula I.

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 derivatives of suitable carboxylic acids are for example anhydrides, chlorides or lower alkyl esters, for example methyl or ethyl esters.

   In these syntheses, suitable esterification catalysts can be used if necessary, such as mineral acids (for example sulfuric acid) or sulfonic acids (for example p-toluenesulfonic acid).



   The reaction can be carried out in a manner known per se, advantageously by adding one of the two starting substances to the second starting substance and mixing the two reaction partners, preferably protected from oxygen. The reaction can be carried out in the presence of a solvent, for example toluene, or also without solvent. The temperature is not critical, it can be between the melting point and the boiling point of the reaction mixture, for example between - 50 and 100 C, preferably between 0 and 50 C. The purification of the product obtained can also be carried out by known methods, for example by washing with water / HCl, extraction with an organic solvent, crystallization and / or chromatography.

   As solvent for the extraction as well as for the chromatographic purification stage, hexane, ethyl acetate or their mixtures are preferred.



   If acid chloride is used as the derivative of the carboxylic acid corresponding to formula V in the reaction, an acid acceptor is advantageously added to the reaction mixture, such as amines such as pyridine or triethylamine. . It is preferred that the amount of the acid acceptor is at least equivalent to the amount of the acid chloride, it is for example from 1 to 2 equivalents, in particular from 1.2 to 1.7 equivalent relative to the chloride acid.



   If the reaction is carried out in the form of a transesterification of an alcohol corresponding to formula IV with the ester of a carboxylic acid corresponding to the

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 formula V, ordinary transesterification catalysts are advantageously added to the reaction mixture. These are for example organic or inorganic bases (for example lithium amide, lithium methylate, potassium hydroxide, etc.) or Lewis acids (for example dibutyl tin oxide) .



   If the carboxylic acid corresponding to formula V and the alcohol corresponding to formula IV are used directly as starting materials, the reaction is advantageously carried out using a water separator, by distilling off the water and / or using reagents which fix the released water, such as for example dicyclohexylcarbodiimide.



   The use of mixtures of carboxylic acids corresponding to formula V or of their derivatives may be of particular practical interest for the preparation of the compounds corresponding to formula I. These mixtures can be used for synthesis in the manner described above , and corresponding mixtures of compounds corresponding to formula I are obtained. Mixtures of compounds corresponding to formula I can 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 corresponding to formula IV for the stabilization of an organic material against oxidative, thermal or actinic degradation, therefore constitute other objectives of the invention.



   The compositions in accordance with the invention preferably contain compounds corresponding to formula IV in which Ri denotes a secondary or tertiary C3-CZ4 alkyl group or Cg-Cg cycloalkyl; and Ru denotes a C1-C1 alkyl or C1-5 cycloalkyl group. We prefer

  <Desc / Clms Page number 10>

 particularly that Ri denotes a secondary or tertiary alkyl group Cs-Cig or cycloalkyl Cg-Cg, for example an isopropyl, sec-butyl, tert-butyl or cyclohexyl, and RI a C3-Cg alkyl, a cycloalkyl Cs-Cg or the methyl group.



   Particularly preferred in the compositions according to the invention are compounds corresponding to formula IV in
 EMI10.1
 which RI denotes a methyl, tert-butyl or cyclohexyl group, in particular a methyl group, and R 'denotes a tert-butyl or cyclohexyl group, in particular tert-butyl.



   The compositions in accordance with the invention preferably contain compounds corresponding to formula IV in which n represents a number between 5 and 8, for example from 6 to 8, in particular the number 6.



   Particular preference is also given, in the compositions in accordance with the invention, to the alcohols corresponding to formula III described below.



   The ro- (hydroxyphenyl) -alkanols corresponding to the formula IV can be prepared by known methods or by analogy with these. Thus, the compounds corresponding to formula IV can be obtained by the process described in US-A-4. 260.832 or by a process analogous thereto. In this process, the appropriate 2,6-substituted phenols are reacted in the presence of an alkali metal, hydroxides or alkali metal alkoxides, at temperatures of 200 to 300 C, with removal of the water formed in the process. during the reaction with a, ro-alkanediols.



   The product can then be isolated by conventional methods and used for the reaction with the derivatives of carboxylic acids corresponding to formula V; however, it is also possible to directly use the crude product without additional purification, for the preparation of compounds corresponding to formula I.



   If used, instead of the starting phenols described in US-A-4,260. 832, a 2,6-disubstituted phenol,

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 among the substituents in which the alkyl or cycloalkyl group is not or is at most a tert-butyl group, new compounds corresponding to formula III are obtained
 EMI11.1
 in which G1 and G1 'have the meanings indicated above for R1 and R1', the meaning "tert-butyl group" being however excluded for G1. As defined above for formula I, n represents an integer between 4 and 8. A compound corresponding to formula III also constitutes one of the objectives of the invention.



   Preferred are compounds corresponding to formula III in which G1 denotes a C3-C24 alkyl group.
 EMI11.2
 secondary or tertiary or Cg-Cg cycloalkyl; and G1 denotes a C1-C1 alkyl or C.sub.5-Ca cycloalkyl group. It is particularly preferred that Go 'denotes a secondary or tertiary Cs-Cis alkyl group or Cg-Cg cycloalkyl, for example an isopropyl, sec-butyl, tert-butyl or cyclohexyl group, and G1 a Cs-Cg alkyl at 1 except the tert-butyl group, or a Cs-Cs cycloalkyl or a methyl group.



   Above all, compounds corresponding to the
 EMI11.3
 formula III in which G1 denotes a methyl or cyclohexyl group, in particular a methyl group, and G1 'denotes a tert-butyl or cyclohexyl group, in particular tert-butyl.



   Compounds corresponding to formula III are preferred in which m is a number between 5 and 8, for example from 6 to 8, in particular the number 6.

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   Other processes by which or in a similar manner to which compounds corresponding to formula III and compounds corresponding to formula IV can be prepared are described or indicated in DE-A-2.147. 544 and NLA-79-05000.



   As described above, the radical A of formula I is derived from a mono carboxylic acid. These can be aromatic, aliphatic, mixed aromatic / aliphatic, cycloaliphatic or bicycloaliphatic acids, or their unsaturated derivatives, for example the following acids: caprylic, acetic, stearic, polyisobutenyl succinic, n-hexacosanic, trimethylacetic, propionic, isovaleric, lauric, oleic, acrylic, methacrylic, sorbic, linoleic, maleic, itaconic, glutaconic, diacids such as oxalic, succinic, isododecylsuccinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic acids 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 nitrilotriacetic acid, of cycloaliphatic acids such as cyclohexane carboxylic acid, 1, 2- and 1,4cyclohexa-dicarboxylic acids and naphthenic acids, among which for example cyclopentane carboxylic acid, cyclopentylacetic acid, 3methylcyclopentylacetic acid, camphoric acid, 4methylcyclohexane carboxylic acid and 2,4, 6trimethylcyclohexane carboxylic acid, bicyclo- acid (2,2,2) -octa-5-ene-2,3-dicarboxylic acid and bicyclo- (2,2,1) -hepta-5-ene-2-carboxylic acid, aromatic carboxylic acids such as benzoic acid, o-, met p-toluic acids, phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, acid
1,2,4,5-benzene-tetracarboxylic acid, diphenic acid,

   1-naphthoic acid, 2-naphthoic acid, naphthalene-1, 8-dicarboxylic acid, naphthalene acid 1,4-

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 dicarboxylic acid, naphthalene-1,4,5-tricarboxylic acid, etc., paraffinic ro-aryl acids such as phenylacetic acid, hydrocinnamic acid, phenylbutyric acid, y- (l-naphthyl) acid -butyric, 8-phenylene-n-valeric acid, # -phenyl-n-capro-n-caproic acid, o-, m- or p-phenylene diacetic acids or o-phenylacetic acid-ss -propionic, as well as unsaturated phenylic acids such as for example cinnamic acid.



   A preferred objective of the invention is represented by the compounds corresponding to formula Ia
 EMI13.1
 in which n is an integer between 4 and 8 and m an integer between 1 and 3, A, in the case where m is equal to 1, represents a C1-Cs alkyl group which is unsubstituted or substituted by a Cg-Cg cycloalkyl group, or else it represents a
 EMI13.2
 C2-C2S alkyl group which is interrupted by a Cg-Cg cycloalkyl group or by one or more of the groups -S -, - 0- and / or-NR2-, or alternatively A, when m is equal to 1, denotes a C 1 -C 6 cycloalkyl group which is unsubstituted or substituted by a C 1 -C 2 alkyl or C 2 -C 12 alkenyl group, a C 1 -C 6 cycloalkenyl group which is unsubstituted or substituted by a C 1 -C 2 alkyl group or C2-C12 alkenyl,

   phenyl, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group, naphthyl, which is unsubstituted or substituted by a C1-Cl2 alkyl or C2-C12 alkenyl group, biphenyl, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group, or a C2-C25 alkenyl group, C6-C1O bicycloalkenyl, C7-C12 phenylalkyl '

  <Desc / Clms Page number 14>

 
 EMI14.1
 C7-C12 phenylalkenyl, Ci-Cig naphthylalkyl, Cn-Cig naphthylalkenyl Cis-Cig biphenylalkyl, Ci-Cia biphenylalkenyl or a group corresponding to formula II:

   
 EMI14.2
 A, when m is equal to 2, denotes a direct bond, a C1-C1 alkylene group, C2-C1 alkenylene, C1-C8 cycloalkylene, which is unsubstituted or substituted by a C1-C1 alkyl group or alkenyl in C2-C12, a C6-Ca cycloalkenylene group, which is unsubstituted or substituted by a C1-Cl2 alkyl or CZ-Cl2 alkenyl group, a C6-Cio bicycloalkenylene group, phenylene, naphthylene or an alkylene group in Cz-Cig interrupted by a Cg-Cg or phenylene cycloalkylene group or by at least one of the groups -S-, -O- or -NR2-;

   A, when m is equal to 3, denotes a (C1-C8 alkane) triyl, (C2-C8 alkene) triyl, benzenetriyl, naphthalenetriyl group; a trivalent group responding to the
 EMI14.3
 R6 formula-R-N-R-or a (C2-Cla) alkane triyl group, which is interrupted by at least one member of the group-S-, -0- or-NR2-; Ru represents a methyl or tert-butyl group; R2 represents an H atom or a C1-C4 alkyl group; R3 and R4 independently denote a C1-C4 alkyl group, and R5, R6 and R7 independently represent a C1-C3 alkylene group
Preferred compounds of formula I are those in which n is an integer between 4 and 8 and m an integer between 1 and 4;

   AT,

  <Desc / Clms Page number 15>

 when m is 1, represents a C1-C2 alkyl group, which is unsubstituted or substituted by a Cg-Cg cycloalkyl group; or it represents a Cz-Czs alkyl group which is interrupted by a Cs-Cg cycloalkyl group or by one or more of the groups -S -, - O- and / or-NR2-; or A, in the case where m is equal to 1, denotes a C 6 -C 6 cycloalkyl group, which is unsubstituted or substituted by a C 1 -C 6 alkyl group; a C6-C8 cycloalkenyl group which is unsubstituted or substituted by a C1-C12 alkyl group; a phenyl group which is unsubstituted or substituted by a C1-Cl2 alkyl group;

   or a C2-C2S alkenyl group; a C7-C12 phenylalkyl group; or a group corresponding to formula II
 EMI15.1
 A, when m is equal to 2, denotes a direct bond; a C1-2 alkylene group; C2-C12 alkenylene; Cs-Cg cycloalkylene, which may be unsubstituted or substituted by a C1-Cis alkyl group; a C6-C8 cycloalkenylene group, which is unsubstituted or substituted by a C1-C6 alkyl group; a phenylene group;

   a divalent heterocyclic radical chosen from furan, thiophene or pyrrole, which is saturated on the nitrogen atom with the hydrogen atom or the substituent-R; or A, when m is equal to 2, denotes a C 1 -C 6 alkylene group interrupted by a C 5 -C 6 or phenylene cycloalkylene group or by at least one of the groups -S-, -O- or -NR2-; and A, when m is equal to 3, denotes a triyl (C1-Ca alkane) group; a (C2-C6 alkene) triyl group; a benzotriyl group; a

  <Desc / Clms Page number 16>

 
 EMI16.1
 R6 trivalent group corresponding to the formula-RS-N-R-; or one
 EMI16.2
 (C2-C1S alkane) triyl group, which is interrupted by at least one of the groups -8-, -0- or -NR2-;

   A, when m is equal to 4, denotes a benzene or cyclohexyl radical having four free valences; Rl and Rl're independently of one another a C1-C1 alkyl group or a Cs-Cg cycloalkyl group; R2 represents an H atom or a C1-C4 alkyl group; R3 and R4 independently of one another denote a C1-C4 alkyl group; and R, R6 and R7 independently of one another represent a C1-C3 alkylene group.



   The compound corresponding to formula I in which R 'is a t-butyl or cyclohexyl group and Ru a methyl, tert-butyl or cyclohexyl group; n is a number between 4 and 6; and A, when m is equal to 1, denotes a C 1 -C 6 alkyl or C 2 -C 12 alkenyl group;
 EMI16.3
 A, when m is equal to 2, denotes a direct bond, a
 EMI16.4
 C1-Cl2 alkylene group; phenylene; S
 EMI16.5
 or a C2-C36 alkylene group interrupted by 1 to 5 oxygen or sulfur atoms; A, when m is equal to 3, denotes a benzenetriyl group
 EMI16.6
 CH2-1 or a trivalent group corresponding to the formula -CHz-N-CHs; and A, when m is equal to 4, denotes a benzene radical having 4 free valences, constitutes a particularly preferred object.



   Among these, compounds which are of particular importance are those in which A, when m is equal to 1, denotes a C2-C12 alkenyl group; and A, in the case where m is equal to 2, denotes a phenylene group;

  <Desc / Clms Page number 17>

 
 EMI17.1
 Ck \ '; a C2-C36 alkylene group interrupted by 1 to 5 oxygen atoms; or a group - (CH2) k-S- (CH2) k-;
 EMI17.2
 and k is an integer from 1 to 3; and in particular the compounds in which m is equal to 1 or 2.



   Particular preference is also given to the compounds corresponding to formula I in which n is an integer between 5 and 8, in particular between 6 and 8, mainly 6.



   Among the compounds corresponding to formula I, compounds which stand out particularly are those corresponding to formula
 EMI17.3
 
 EMI17.4
 in which A denotes - (CH2) j-; - (CH2) k-S- (CH2) k S
 EMI17.5
 or- (CH2) 2-0- [(CH2) 2-0-] j- (CH2) 2-; j is 0 or an integer between 1 and 4; and k denotes an integer between 1 and 3.



   Compounds of predominant importance are in particular the following: a) 6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl stearate;
 EMI17.6
 b) 6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl stearate; c) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl succinate; d) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl adipate; e) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl suberate;

   

  <Desc / Clms Page number 18>

 f) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl isophthalate; g) bis- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl isophthalate; h) tris- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl trimellitate; j) tris- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl trimellitate; k) tris- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl trimellitate;

     1) tris- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl trimesinate corresponding to the formulas
 EMI18.1
 

  <Desc / Clms Page number 19>

 
 EMI19.1
 

  <Desc / Clms Page number 20>

 
 EMI20.1
 
Compounds of particular technical importance are the compounds of formula I, in which n is an integer between 4 and 6; in particular those in which n is an integer between 4 and 6 and in which A, when m is equal to 1, denotes a C6-C20 alkyl group, A, when m is equal to 2, denotes a direct bond, a C1-C10 alkylene group, phenylene, or C2-C6 alkylene interrupted by -S-, and A, in the case where m is equal to 3, denotes a benzenetriyl group.



   A preferred subject of the invention further consists of the compounds corresponding to formula I in

  <Desc / Clms Page number 21>

 which m is equal to 2 and A denotes an alkylene group in
C4-C36 interrupted by at least one oxygen atom.



   Compounds corresponding to formula I of interest are also those in which A, when m is equal to
1, denotes a Cg-Cso alkyl group; Cs-Cig alkenyl; Cg-Csg alkyl interrupted by one or more of the groups -S- or -O-, a cyclohexyl group, a cyclohexyl group substituted by a C1-C4 alkyl group, a phenyl group, a phenyl group substituted by a alkyl group in Cl-Cl2 or a phenylalkyl group having in total 7 to 9 carbon atoms;

  
A, in the case where m is equal to 2, denotes a direct bond, a C1-C1 alkylene group, Cz-Ciz alkenylene, phenylene or C2-C36 alkylene interrupted by a -S- or -O- group, and
A, when m is equal to 3, denotes a group (C1-C6 alkane) triyl, benzenetriyl, C7-C1O alkylbenzenetriyl '
 EMI21.1
 CH2- 1 or -CH2-N-CH2--
The compounds corresponding to formula I are suitable for stabilizing organic materials with respect to thermal, oxidative and actinic degradation; particular emphasis should be placed on the remarkable action as antioxidants in the stabilization of organic matter.



   Examples of such materials are: 1. Polymers of mono and diolefins, for example
 EMI21.2
 polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene as well as polymers of cycloolefins such as for example those of cyclopentene or norbornene; and also polyethylene (which can if necessary be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (PELbd), low density branched polyethylene (PERbd).

  <Desc / Clms Page number 22>

 



   Polyolefins, i.e. polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various methods, in particular by methods following: a) by radical route (usually under high pressure and high temperature); b) by means of a catalyst, the catalyst ordinarily containing one or more metals from groups IVb, Vb, VIb 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 may be
 EMI22.1
 coordinated either by n bonds or by cr bonds.

   These metal complexes can be free or fixed on a support, for example on activated magnesium chloride, on titanium chloride III, on aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or else other activators can be used, such as, for example, alkyl metals, metal hydrides, alkyl metal halides, oxides of alkyl metals or alkyloxane metals, metals being elements of groups Ia, IIa and / or IIIa. The activators can for example be modified with other ester, ether, amine or silyl ether groups.

   These catalyst systems are usually known as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or Single Site (SSC) catalysts.



  2. Mixtures of the polymers indicated in 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene

  <Desc / Clms Page number 23>

 (e.g. PP / HDPE, PP / LDPE) and mixtures of various types of polyethylenes (e.g. LDPE / HDPE).



  3. Copolymers of mono and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LDPE) and mixtures of these with low density polyethylene ( LDPE),
 EMI23.1
 propylene-butene-1 copolymers, propyleneisobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene butadiene copolymers, isobutylene-isoprene copolymers , ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene vinyl acetate copolymers and their copolymers with carbon monoxide,

   or ethylene-acrylic acid copolymers and their salts (ionomers), as well as tertpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and in addition mixtures of these copolymers with each other and with the polymers indicated in 1, for example propylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, PELbd copolymers / ethylene-vinyl acetate, PELbd / ethylene-acrylic acid copolymers and alternating or random polyalkylene / carbon monoxide copolymers and their mixtures with other polymers, for example polyamides.



  4. Hydrocarbon resins (for example Cg-Cg), including their hydrogenated variants (by adhesive resins) and mixtures of polyalkylenes and starch.

  <Desc / Clms Page number 24>

 



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



  6. Copolymers of styrene or of α-methylstyrene with dienes or acrylic derivatives, such as for example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene acrylate and methacrylate d 'alkyl, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; mixtures with high impact resistance in copolymers of styrene and another polymer, such as for example a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, such as for example styrenebutadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene or styrene-ethylene / propylene-styrene.



  7. Graft copolymers of styrene or of α-methylstyrene, such as for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitril (or methacrylonitrile) on polybutadiene ; styrene, acrylonitril and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitril and maleic anhydride or maleimide on polybutadiene;

   styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and
 EMI24.1
 acrylonitril on ethylene-propylenediene terpolymers, styrene and acrylonitril on alkyl polyacrylates or polymethylmethacrylates, styrene and acrylonitril on acrylate-butadiene copolymers, as well as their mixtures with the indicated copolymers in 6), which are known for example under the names of polymers ABS, MES, ASA or AES.

  <Desc / Clms Page number 25>

 



  8. 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 halogenated vinyl compounds, such as for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; as well as their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.



   9. Copolymers derived from acids (X. P-unsaturated and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates modified to increase their impact resistance by butyl acrylate, polyacrylamides and polyacrylonitriles.



   10. 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, copolymers acrylonitrile-vinyl halide or acrylonitrile-alkyl butadiene methacrylate terpolymers.



   11. Polymers which are derived from unsaturated alcohols and amines or their acylated derivatives or their acetals, such as
 EMI25.1
 polyvinyl alcohol, polyacetate, -stearate, -benzoate, polyvinyl maleate, polyvinyl butyral, allyl polyphthalate, polyallyl melamine; as well as their copolymers with the olefins indicated in point 1).

  <Desc / Clms Page number 26>

 12. Homo-and copolymers of cyclic ethers such as polyalkylene glycols, polyoxyethylenes, polyoxypropylenes or their copolymers with bisglycidyl ethers.



  13. Polyacetals, such as polyoxymethylene, as well as polyoxymethylenes which contain comonomers, such as ethylene oxide; polyacetals which are modified by thermoplastic polyurethanes, acrylates or MES.



  14. Poly (phenylene oxides and sulfides) and their mixtures with styrene polymers or polyamides.



  15. Polyurethanes which are derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups, on the one hand, and aliphatic or aromatic polyisocyanates on the other hand, as well as their intermediate products.



  16. Polyamides and copolyamides which are 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, an elastomer as modifier, for example poly-2,4, 4-trimethylhexamethylene-terephthalamide or poly-m-phenylene -isophthalamide.

   Block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or elastomers chemically linked or grafted; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. And also with polyamides or

  <Desc / Clms Page number 27>

 copolyamides modified by EPBM or ABS; as well as polyamides condensed during processing ("RIM" polyamide systems).



  17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.



  18. Polyesters which are derived from dicarboxylic acids and dialcohols, and / or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexaneterephthalate, polyhydroxybenzoates as well as polyether- block esters which are derived from polyethers having hydroxyl end groups, and also polyesters modified with polycarbons or MES.



  19. Polycarbonates and polyester carbonates.



  20. Polysulfones, polyether sulfones and polyether ketones.



  21. Crosslinked polymers which are derived, on the one hand, from aldehydes and, on the other hand, from phenols, urea or melamine, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins .



   22. Drying or non-drying alkyd resins.



   23. 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 halogenated variants, which are not very combustible.



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

  <Desc / Clms Page number 28>

 epoxy-acrylates, urethane-acrylates or polyester-acrylates.



  25. Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.



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



  27. Natural polymers, such as cellulose, natural rubber, gelatins and their homologous derivatives of chemically modified polymers, such as cellulose acetates, propionates and butyrates or cellulose ethers such as methyl cellulose; and also rosin resins and their derivatives.



  28. Polyblends of the above 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 / PEhd, 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 ester-based oils, fats and waxes synthetics (e.g. phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any weight ratio, as used for spinning preparations, and their emulsions watery.

  <Desc / Clms Page number 29>

 30. Aqueous emulsions of natural or synthetic rubbers, such as a natural rubber latex or latexes of styrene / butadiene carboxylated copolymers.



   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 matter against oxidative, thermal or actinic degradation.



   The invention therefore also includes a process 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.



   The use of compounds corresponding to formula I as antioxidants in synthetic organic polymers 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 points 1) to 3) and in points 5) and 6), in particular polyethylene and polypropylene as well as ABS and styrene copolymers -butadiene. Preferred objects of the invention are therefore compositions in which the organic material is a synthetic organic polymer or a mixture of these polymers, in particular 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 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% relative to the total weight of the material to be stabilized. We particularly prefer to use

  <Desc / Clms Page number 30>

 the compounds according to the invention in amounts of 0.01 to 0.5%, better still from 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. Anti-oxidants 1.1 Alkylated mono-phenols, for example:
2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol,
2,6-di-tert-butyl-4-ethylphenol,
2, 6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -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,
 EMI30.1
 2,4-dimethyl-6- (1'-methyl-undéc-l'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2, 4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.



  1.2 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-4-nonylphenol.



  1.3 Hydroquinones and alkylated hydroquinones, for example:
2,6-di-tert-butyl-4-methoxy-phenol,
2,5-di-tert-butyl-hydroquinone,
2,5-di-tert-amyl-hydroquinone,
2,6-diphenyl-4-octadecyloxy-phenol,
2,6-di-tert-butyl-hydroquinone,
2,5-di-tert-butyl-4-hydroxyanisole,

  <Desc / Clms Page number 31>

 
 EMI31.1
 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate 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-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3, 6-di-sec-amylphenol) and 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.



  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- [4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2 '-methylene-bis- (6-nonyl-4-methylphenol), 2, 2'-methylene-bis- (4, 6-di-tert-butylphenol), 2, 2'-ethylidene-bis- (4, 6 -di-tert-butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (a-methylbenzyl) -4-nonylphenol ], 2,2'-methylene-bis- [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4, 4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1, 1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis- (3 -tert-butyl-5-methyl-2-hydroxybenzyl) -4methylphenol, 1, 1,

   3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis- (S-tert-butyl-4-hydroxy-2-methylphenyl) -3-ndodecylmercapto-butane, Ethylene -glycol-bis- [3,3-bis- (3'-tertbutyl-4'-hydroxy-phenyl) butyrate],

  <Desc / Clms Page number 32>

   bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) - dicyclopentadiene,
 EMI32.1
 bis- [2- (3'-tert-butyl-2'-hydroxy-5'methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate], 1, 1-bis- (3, 5-dimethyl-2 -hydroxyphenyl) -butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl ) -4-ndodecylmercapto-butane and 1, 1, 5, 5-tetra- (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -pentane, 1.6 Oxygenated, nitrogenous and S-benzylated compounds, for example :

   3.5, 3 ', 5'-tetra-tert-butyl-4, 4'-dihydroxy-dibenzyl ether,
Octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,
 EMI32.2
 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-4-hydroxybenzyl) sulfide and 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate).



  1.7 Hydroxybenzylated malonates, for example:
2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -dioctadecyl malonate,
 EMI32.3
 Dioctadecyl, 2,2-bis ((3,5-di-tert-butyl-4-hydroxybenzyl) -dodecylmercaptoethylmalonate and 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -dioctadecyl malonate
2, 2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate di- [4- (1, 1, 3, 3-tetramethylbutyl) -phenyl].



  1.8 Hydroxybenzyl aromatic hydrocarbons, for example:
1, 3, 5-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -
2,4,6-trimethylbenzene,

  <Desc / Clms Page number 33>

 
1,4 bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6,6 tetramethylbenzene and
2,4,6-tris-93,5-di-tert-butyl-4-hydroxybenzyl) - phenol.



  1.9 Triazine compounds, for example:
 EMI33.1
 2, 4-bis-octylmercapto-6- (3, 5-di-tert-butyl-4hydroxyanilino) -l, 3, 5-triazine, 2-octylmercapto-4, 6-bis- (3, 5-di-tert -butyl-4hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4hydroxyphenoxy) -1,3,5-triazine 2,4,4 6-tris- (3, 5-di-tert-butyl-4-hydroxyphenoxy) - 1, 2, 3-triazine, isocyanurate of 1, 3, 5-tris- (3, 5-di-tert-butyl-4hydroxybenzyle ), 1, 3, 5-tris- (4-di-tert-butyl-3hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2, 4, 6-tris- (3, 5-di-tert-butyl-4 -hydroxyphenylethyl) - 1, 3, 5-triazine, 1, 3, 5-tris- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3, 5-triazine and isocyanurate of 1, 3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl).



  1.10 Benzyl phosphonates, for example: 2,5-dimethyl-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, phosphonate of dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate and Ca salt of 3,5 monoethyl ester of acid - di-tert-butyl-4-hydroxybenzyl-phosphonic.



  1.11 Acylaminophenols, for example: 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide and

  <Desc / Clms Page number 34>

 N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester.



  1.12 Esters of B- (3 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono- or polyalcohols, for example: methanol, ethanol, octadecanol, 1 , 6- hexane-diol, 1,9-nonane-diol, ethylene-glycol, 1,2-propane-diol, neopentylglycol, thio-diethylene-glycol, diethylene-glycol, triethylene-glycol , pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis-
 EMI34.1
 (hydroxyethyl) -oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane-diol, trimethylol-propane and 4-hydroxymethyl-1-phospha-
2,6,7-trioxabicyclo- [2. 2.2] octane.



  1.13 Esters of ss- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono- or polyalcohols, for example: methanol, ethanol, octadecanol, 1, 6- hexane-diol, 1,9-nonane-diol, ethylene-glycol, 1,2-propane-diol, neopentylglycol, thio-diethylene-glycol, diethylene-glycol, triethylene- glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) -oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexane-diol, trimethylol-propane and 4-hydroxymethyl-1-phospha-
2,6,7-trioxabicyclo- [2. 2.2] octane.



  1.14 Esters of ss- (3 5-dicyclohexyl-4-hydroxyohényl) -propionic acid with mono or polyalcohols, for example: methanol, ethanol, octadecanol, 1,6-hexane -diol, 1,9-nonane-diol, ethylene-glycol, 1,2-propane-diol, neopentylglycol, thio-diethylene-glycol, diethylene-glycol, triethylene-glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis-

  <Desc / Clms Page number 35>

 (hydroxyethyl) -oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexane-diol, trimethylol-propane and 4-hydroxymethyl-1-phospha-
2,6,7-trioxabicyclo- [2. 2.2] octane.



  1.15 Esters of (3,5-di-tert-butyl-4-hydroxv-phenyl) -acetic acid with mono-or poly-alcohols, for example: methanol, ethanol, octadecanol, 1,6-hexane-diol, 1,9-nonane-diol, ethylene-glycol, 1,2-propane-diol, neopentylglycol, thio-diethylene-glycol, diethylene-glycol, triethylene- glycol, pentaerythritol,
 EMI35.1
 tris- (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) -oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane-diol, trimethylol-propane and 4-hydroxymethyl-1 -phospha- 2, 6, 7-trioxabicyclo- [2. 2.2] octane.



  1. 16 H- (3,5-di-tert-butyl-4hydroxyphenyD-propionic acid amides, for example: N, N'-bis- (3, S-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylene diamine, N, N'-bis- (3, S-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylene diamine and
N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.



  2. UV absorbers and light protection agents 2.1 2- (2'-Hydroxyphenyl) -benzotriazoles, for example:
 EMI35.2
 2- (2'-hydroxy-S'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -benzo-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-chlorobenzotriazole,

  <Desc / Clms Page number 36>

   2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5- chloro-benzotriazole,
 EMI36.1
 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) -benzotriazole, 2- (3 ', 5'-di -tert-amyl-2'-hydroxyphenyl) -benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) - benzotriazole,

   a mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2octyloxycarbonylethyl) -phenyl) -5-chloro-benzotriazole,
 EMI36.2
 2- (3-tert-butyl-5- [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- [2- (2 -ethylhexyloxy) -carbonyl- ethyl) -2'-hydroxy-phenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (3'-tert-butyl- 2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) -phenyl) -benzotriazole, 2, 2'-methylene-bis- [4- (1, 1,3, 3-tetramethylbutyl) -6- benzotriazol-2 -yl-phenol],

   2- (3'-ter-) transesterification product
 EMI36.3
 butyl-5- (2-methoxycarbonylethyl) -2-hydroxyphenyl] -benzotriazole with polyethylene glycol 300, [R-CH2CH2 -COO (CH2) 3] 2 with R = 3'-tert-butyl-4-hydroxy-5 '-2H-benzotriazol-2-yl-phenyl.



  2. 2 2-Hydroxybenzophenones, for example:

  <Desc / Clms Page number 37>

 4-hydroxylated, 4-methoxylated, 4-octyloxylated derivatives,
4-decyloxylated, 4-dodecyloxylated, 4-benzyloxylated,
4, 2 ', 4'-trihydroxylated and 2'-hydroxy-4, 4'-dimethoxylated.



  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-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate
3,5-di-tert-butyl-4-hydroxybenzoate of hexadecyl,
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:
 EMI37.1
 a-cyano-H, ethyl ss-diphenylacrylate, a-cyano-B, iso-octyl ss-diphenylacrylate, methyl a-methoxycarbonyl-cinnamate, a-cyano-ss-methyl-p-methoxy-cinnamate butyl methyl, a-cyano-ss-methyl-p-methoxy-cinnamate, methyl a-methoxycarbonyl-p-methoxy-cinnamate and N- (ss-methoxycarbonyl-ss-cyanovinyl) -2-methylindoline.



  2.5 Nickel compounds, for example: - nickel complexes derived from 2, 2'-thio-bis- [4- (1,1, 3, 3-tetramethylbutyl) -phenol], for example the 1: 1 complex or the 1: 2 complex, possibly with other ligands, such as n-butylamine, triethanolamine or
N-cyclohexyl-diethanolamine, - nickel dibutyl-dithiocarbamate, nickel salts of mono-alkyl esters of 4-hydroxy-3,5-di-tert-butyl-benzylphosphonic acid, such as methyl and ethyl esters ,

  <Desc / Clms Page number 38>

 - nickel complexes derived from ketoximes, such as 2-hydroxy-4-methyl-phenyl-undecylketoxime, and - nickel complexes from 1-phenyl-4-lauroyl-5-hydroxypyrazole, possibly with additional ligands.



  2.6 Sterically hindered amines, for example: bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (2,2,6,6-tetramethylpiperidyl succinate), bis- (l, 2, sebacate) 2,6,6-pentamethylpiperidyl),
 EMI38.1
 n-butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate bis- (1,2,2,6,6-pentamethylpiperidyl), 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
 EMI38.2
 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, nitrilotriacetate of tris- (2, 2, 6, 6-tetramethyl-4-piperidyl), 1,2, 3,4-butane -tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -tetracarboxylate, 1, 1'- (1, 2-ethanediyl) -bis- (3, 3,5,

   5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis-1, 2,2, 6, 6-4-pentamethylpiperidyl malonate ) -2-
 EMI38.3
 n-butyl- (2-hydroxy-3, 5-di-tert-butylbenzyl) 3-n-octyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro- [4.

   5] decane-2, 4-dione, bis- (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis- (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl succinate) ), condensation product of N, N'-bis- (2, 2,6, 6-bis-tetramethyl-4-piperidyl) -hexamethylenediamine with 4-morpholino-2, 6-dichloro-1,3,5 -triazine,

  <Desc / Clms Page number 39>

 
 EMI39.1
 condensation product of 2-chloro-4, 6-di- (4-nbutylamino-2, 2, 6, 6-tetramethylpiperidyl) -1, 3, 5triazine with 1, 2-bis- (3-aminopropylamino) - ethane, condensation product of 2-chloro-4, 6-di- (4-nbutylamino-1, 2, 2, 6, 6-pentamethylpiperidyl) -1, 3, 5triazine with 1, 2-bis- (3 -aminopropylamino) - ethane, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8triazaspiro- [4.

   5] 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,
 EMI39.2
 2. 7 Oxalamides, for example: 4, 4'-dioctyloxy-oxalanilide, 2, 2'-dioctyloxy-5, 5'-di-tert-butyl-oxalanilide, 2, 2'-didodecyloxy-5, 5'-di -tert-butyl-oxalanilide, 2-ethoxy-2'-ethyl-oxalanilide,
 EMI39.3
 N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxalanilide, mixtures of the latter with 2-ethoxy-2'-ethyl-
5, 4'-di-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-Hydroxyr) hényl) -1,3.5-triazines, for example:
2,4, 6-tris- (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine,
 EMI39.4
 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4dimethylphenyl) -1,3,5-triazine 2- (2,4,4-dihydroxyphenyl) -4,6-bis- (2 , 4dimethylphenyl) -1,3,5-triazine, 2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4dimethylphenyl) -1,3,5-triazine 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis- (4-methylphenyl) -1,3,5-triazine,

  <Desc / Clms Page number 40>

 
 EMI40.1
 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis- (2, 4dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy- propyloxy) - phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) - phenyl ] -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,
 EMI40.2
 N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis- (benzylidene-hydrazide) of oxalic acid , oxanilide, dihydrazide of isophthalic acid, bis-phenylhydrazide of sebacic acid, di-hydrazide of N acid, N'-diacetal-adipic, di-hydrazide of N acid, N'-bis-salicyloyl -oxalic and di-hydrazide of N, N'-bis-salicyloylthiopropionic acid.



  4. Other phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and 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,

  <Desc / Clms Page number 41>

 bis- (2,6-di-tert-butyl-4methylphenyl) -pentaerythritol diphosphite, bis- (isodecyloxy-pentaerythritol diphosphite, bis- (2,4-di-tert-butyl-6-methylphenyl) diphosphite -pentaerythritol, bis- (2, 4, 6-tri-tert-butylphenyl) diphosphite - pentaerythritol, tristearyl-sorbitol triphosphite,

   tetrakis- (2,4-di-tert-butylphenyl) - 4,4'-biphenylene diphosphite,
 EMI41.1
 6-isooctyloxy-2, 4, 8, 10-tetra-tert-butyl-12Hdibenz [d, g] -l, 3, 2-dioxaphosphocine, 6-fluoro-2, 4, 8, 10-tetra-tert-butyl -12-methyl-dibenz [d, g] -1, 3,2-dioxaphosphocine, bis- (2,4-di-tert-butyl-6-methylphenyl) phosphite - methyl and bis- (2,4) phosphite -di-tert-butyl-6-methylphenyl).



  5. Peroxide destroyers, for example: esters of ss-thiodipropionic acid, such as lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide pentaerythritol tetrakis- (ss-dodecylmercapto) -propionate.



  6. Polyamide stabilizers, for example: copper salts associated with iodides and / or phosphorus compounds, and salts of divalent manganese.



  7. Basic co-stabilizers, for example:

  <Desc / Clms Page number 42>

 melamine, poly- (vinylpyrrolidone), cyanoguanidine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali or alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate or potassium palmitate, antimony pyrocatecholate and tin pyrocatecholate.



  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.



  10. Other additives, for example: plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic and porogenic.



  11. 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% relative to the total weight of the material to be stabilized.



   The incorporation of the compound corresponding to formula I and, where appropriate, other additives into the organic material is carried out by known methods.



  The incorporation into the materials can for example be

  <Desc / Clms Page number 43>

 carried out by mixing or applying the compounds corresponding to formula I, and where appropriate other additives, by the usual methods in the art.



  In the case of polymers, in particular synthetic polymers, the incorporation can take place before or during the shaping, or by application of the compounds dissolved or dispersed on the polymer, with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized in the form of latex.



  Another possibility of incorporating the compounds corresponding to formula I into the polymers consists in adding them before, during or immediately after the polymerization of the corresponding monomers or before crosslinking. The compounds corresponding to formula I can be added in this case as such, but also in encapsulated form (for example in waxes, oils or polymers).



  In the case of addition before or during the polymerization, the compounds corresponding to formula I can act as regulators of the chain length of the 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, with the 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 mastics.



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

  <Desc / Clms Page number 44>

 



  EXAMPLE 1: Preparation of 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -butanol
50 g of potassium hydroxide, 316 g of 2-tert-butyl-6-methylphenol and 866 g of 1,4-butane diol are introduced into an autoclave. After passing nitrogen, the autoclave is closed and the mixture is heated to 235 ° C. (under 4 bar) with stirring, for 6 hours; a further increase in pressure is prevented as a result of the reaction by allowing gas to escape. When the reaction is complete, the mixture is cooled to 80 ° C. and the autoclave is removed. The excess butane diol is removed by distillation. The distillation residue 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
 EMI44.1
 (310 g) contains the title product meeting the
 EMI44.2
 formula: OH OH (CH3hC '/' 1 1 (CHCCHs CH2, Chu zoo C 2 CH2 CH2 at 68-70%. The additional purification is carried out by fractional distillation under vacuum. The crude product boils at 115 OC at 35 Pa ( = 0.35 mbar). It has an index of
 EMI44.3
 refraction no = 1, 5322.



  20 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-butane diol, an equivalent amount of 1,6-hexane-diol is used. The product obtained,
 EMI44.4
 having the formula: OH (CLcH, 11 (CH2) 6- OH

  <Desc / Clms Page number 45>

 it has a boiling point at 35 Pa (= 0.35 mbar) of 135 C and melts at 45 C.



  EXAMPLE:
To a solution of 18.9 g (80 mmol) of 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -butanol (product of Example la) 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 20-25 ° C., it is filtered, the filtrate is poured into aqueous HCl about 1M and extracted with ethyl acetate. After drying and concentrating the organic phase, the crude product obtained is purified by chromatography (SiO2; hexane: ethyl acetate = 19: 1). 37.2 g (93%) of the product corresponding to the formula are obtained:
 EMI45.1
 (compound 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 n 2 to 16, the ro- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -alkanols are first prepared by synthesis, by the method described in Example 1a. or the corresponding ru- (3,5-di-tert-butyl-4-hydroxyphenyl) -alkanols. The starting compounds thus obtained (compounds corresponding to formula IV) are then transformed, using the corresponding acid chlorides, by the process described in Example 1c, into the indicated end products (compounds corresponding to the

  <Desc / Clms Page number 46>

 formula I). The indications on the purity and the characterization of the compounds are collated in Tables 1 and 2. When no melting point is indicated, the compounds are liquid at room temperature.



   TABLE 1
IR compositions and data for compounds 1 to 8
 EMI46.1
 OH (CHgCCHs Type of compound: tu Il (CH2-0 ---- A
 EMI46.2
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> COMPOSITION <SEP> IR <SEP>: <SEP> 1 / #
 <tb> n <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> 0
 <tb> calc. <SEP> found <SEP> calc. <SEP> found <SEP> [cm-l]
 <tb> 1 <SEP> 4 <SEP> -n-C17H35 <SEP> 78.8 <SEP> 78.7 <SEP> 11.6 <SEP> 11, <SEP> 4 <SEP> 1738
 <tb> 2 <SEP> 4 <SEP> -n-C7H1S <SEP> 76.2 <SEP> 76.1 <SEP> 10.6 <SEP> 10.6 <SEP> 1719
 <tb> 3 <SEP> 4-i-C7Hi5 <SEP> 76.2 <SEP> 76.2 <SEP> 10.6 <SEP> 11.0 <SEP> 1717
 <tb> 4 <SEP> 4 <SEP> -i-C12H25 <SEP> 77.7 <SEP> 77.7 <SEP> 11.2 <SEP> 11.1 <SEP> 1717
 <tb> 5 <SEP> 4 <SEP> -i-C7H15 <SEP> 76.2 <SEP> 76.0 <SEP> 10.6 <SEP> 10.4 <SEP> 1715
 <tb> C2H5
 <tb> 6 <SEP> 6 <SEP> -CH2-CH-CH2-C2H5- <SEP> 76, <SEP> 9 <SEP> 76.9 <SEP> 10.8 <SEP> 10.6 <SEP> 1715
 <tb> 7 <SEP> 6 <SEP> -n-C11H23 <SEP> 78.0 <SEP> 77.9 <SEP> 11.3 <SEP> 11.5 <SEP> 1732
 <tb> 8 <SEP> 6 <SEP> -n-C17H35 <SEP> 79.2 <SEP> 79.1 <SEP> 11, <SEP> 8 <SEP> 12.2 <SEP> 1720
 <tb>
 (See table 2 next page)

   

  <Desc / Clms Page number 47>

 
TABLE 2 Melting point, IR compositions and data
 EMI47.1
 for compounds 9 to 16
 EMI47.2
 OH (CHcJC (CH Type of compound: (CH3hC'Q'C (CH3h si (CHn-O --- A
 EMI47.3
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> F <SEP> COMPOSITION <SEP> IR <SEP>: <SEP> 1 / Â.
 <tb> n <SEP> [C] <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> 0
 <tb> calc. <SEP> found <SEP> calc. <SEP> found <SEP> [cm ']
 <tb> C2H5
 <tb> 9 <SEP> 4 <SEP> -CH2-CH-CH2-C2H5- <SEP> - <SEP> 77, <SEP> 2 <SEP> 77.0 <SEP> 11, <SEP> 0 <SEP> 10.8 <SEP> 1732
 <tb> 10 <SEP> 4-n-C7H15 <SEP> -77, <SEP> 2 <SEP> 77, <SEP> 2 <SEP> 11.0 <SEP> 11.4 <SEP> 1736
 <tb> 11 <SEP> 4-i-C12H25-78, <SEP> 4 <SEP> 78.3 <SEP> 11.5 <SEP> 11.5 <SEP> 1735
 <tb> 12 <SEP> 4 <SEP> -n-C17H35 <SEP> 30-33 <SEP> 79.4 <SEP> 79.5 <SEP> 11.8 <SEP> 12.1 <SEP> 1738
 <tb> 13 <SEP> 5 <SEP> -n-C17H35 <SEP> 31-32 <SEP> 79.5 <SEP> 79, <SEP> 6 <SEP> 11.9 <SEP> 11, <SEP> 9 <SEP> 1738
 <tb> C2Hg
 <tb> 14 <SEP> 6 <SEP> -CH2-CH-CH2-C2H5- <SEP> - <SEP> 77.7 <SEP> 77.7 <SEP> 11.2 <SEP> 11.5 <SEP> 1738
 <tb> 15 <SEP> 6 <SEP> -n-C11H23 <SEP> - <SEP> 78, <SEP> 6 <SEP> 78.5 <SEP> 11, <SEP> 6 <SEP> 11, <SEP> 9 <SEP> 1737
 <tb> 16 <SEP> 6 <SEP> -n-C17H3S <SEP> 35 <SEP> 79,

    <SEP> 7 <SEP> 79, <SEP> 6 <SEP> 12, <SEP> 0 <SEP> 12, <SEP> 2 <SEP> 1738
 <tb>
 EXAMPLE 17
A colorless solution of 33 g is added dropwise to a 350 ml sulfonation flask.
 EMI47.4
 (0.14 mole) of the product of Example 1a and 16.6 g (0.21 mole) of pyridine in 200 ml of toluene, at 10 ° C., under nitrogen, of 13.6 g (0.074 mole) of adipic acid dichloride. The mixture is then allowed to warm to room temperature while continuing to stir. After 2 hours, the reaction mixture is poured onto aqueous hydrochloric acid and extracted with ethyl acetate. After drying and concentrating the organic phase, the product is purified

  <Desc / Clms Page number 48>

 crude obtained by chromatography (Si02; hexane: ethyl acetate = 19: 1).

   36 g (88%) of the product are obtained
 EMI48.1
 (compound 17) corresponding to the formula:
 EMI48.2
 
 EMI48.3
 melting at 50-52 C. The characterization (IR) and the composition are given in table 3.



  EXAMPLES 18-22 AND 24-34
For the preparation of compounds n 18 to 22 and 24 to 34, the (0- (3-tert-butyl-5-methyl-4-) is first prepared by synthesis, by the method described in Example 1a.
 EMI48.4
 hydroxyphenyl) -alkanols or the corresponding (0- (3, 5-di-tert-butyl-4hydroxyphenyl) -alkanols. The starting materials thus obtained (compounds corresponding to formula IV) are then transformed, using the dichlorides of Corresponding dicarboxylic acids by the process described in Example 1a, into the end products indicated (compounds corresponding to formula I) The indications on the purity and the characterization of the compounds obtained are collated in Tables 3, 4 and 5.



  EXAMPLE 23
In a 750 ml sulfonation flask, 4.98 g (30 mmol) of isophthalic acid, 14.4 g (70 mmol = 2.3 equivalents) of dicyclohexylcarbodiimide and 150 are mixed at 20-25 ° C., under nitrogen. ml of dichloromethane. The white suspension obtained is added to a solution of 15.9 g (60 mmol = 2 equivalents) of 6- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -hexanol (product of Example Ib) in 80 ml of dichloromethane and a solution of 0.73 g (6 mmol) of dimethylaminopyridine in 5 ml of dichloromethane. The mixture is heated at reflux for

  <Desc / Clms Page number 49>

 4 hours. It is then cooled to 20-25 C, filtered and evaporated. The crude product obtained (viscous oil) is purified by chromatography (SiO2; hexane / ethyl acetate = 19: 1).

   11.3 g (57%) of compound 23 are obtained in the form of a colorless oil. Information on purity and characterization is given in Table 3.



   TABLE 3
Melting points, compositions and IR data
 EMI49.1
 for compounds n 17 to 23
 EMI49.2
 OH OH (CHCJCH, CH, Lc (CH,), Type of compound: 0 0 h Il Il (CH2) n-0-8 - A-8-0- (CH2) n
 EMI49.3
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> F <SEP> COMPOSITION <SEP> IR <SEP>: 1 / #
 <tb> n <SEP> [OC] <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> 0
 <tb> wedge. <SEP> found <SEP> wedge. <SEP> found <SEP> [cm-1]
 <tb> 17 <SEP> 4- <SEP> (CH2) <SEP> 4- <SEP> 50-52 <SEP> 74.2 <SEP> 73.8 <SEP> 09.3 <SEP> 09.5 <SEP> 1718
 <tb> 18 <SEP> 4- <SEP> (CH2) <SEP> 8--75, <SEP> 2 <SEP> 74.7 <SEP> 09.8 <SEP> 09.9 <SEP> 1717
 <tb> 19 <SEP> 6--74, <SEP> 2 <SEP> 74.1 <SEP> 09.3 <SEP> 09.7 <SEP> 1738
 <tb> 20 <SEP> 6 <SEP> - <SEP> (CH2) <SEP> 2- <SEP> 90-103 <SEP> 74.7 <SEP> 73.9 <SEP> 09.6 <SEP> 09.8 <SEP> 1713
 <tb> 21 <SEP> 6 <SEP> - (CH2) 4- <SEP> 91-95 <SEP> 75.2 <SEP> 75.0 <SEP> 09.8 <SEP> 09.7 <SEP> 1718
 <tb> 22 <SEP> 6- <SEP> (CHg - 76, <SEP> 0 <SEP> 75.5 <SEP> 10.2 <SEP> 10.2 <SEP> 1718
 <tb> 23 <SEP> 6 <SEP> # <SEP> - <SEP> 76, <SEP> 6 <SEP> 76, <SEP> 1 <SEP> 08, <SEP> 9 <SEP> 09.1 <SEP> 1723
 <tb>
 (See table 4 next page)

  <Desc / Clms Page number 50>

 
 EMI50.1
 TABLE 4 Melting point,

   IR compositions and data for compounds # 24 to 30
 EMI50.2
 OH OH (CHcJC (CH (CHcJC (CH Type of compound: '/ 1 T T (CHr-O-C - A - 0- (CH2) n
 EMI50.3
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> F <SEP> COMPOSITION <SEP> IR: 1 / #
 <tb> nO <SEP> [C] <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> O
 <tb> wedge. <SEP> found <SEP> wedge. <SEP> found <SEP> [cm-1]
 <tb> 24 <SEP> 4 <SEP> - (CH2) 4- <SEP> 86-88 <SEP> 75.6 <SEP> 75.5 <SEP> 10.0 <SEP> 09.8 <SEP> 1734
 <tb> 25 <SEP> 5 <SEP> - <SEP> 89-90 <SEP> 75.2 <SEP> 75.1 <SEP> 09.8 <SEP> 09.9 <SEP> 1743
 <tb> 26 <SEP> 5- <SEP> (CH2) <SEP> 4- <SEP> 92-95 <SEP> 76.0 <SEP> 75.6 <SEP> 10.2 <SEP> 10.0 <SEP> 1735
 <tb> 27 <SEP> 6 <SEP> - <SEP> - <SEP> 75, <SEP> 6 <SEP> 75.7 <SEP> 10.0 <SEP> 10.1 <SEP> 1743
 <tb> 28 <SEP> 6- <SEP> (CH2) <SEP> 2- <SEP> 70 <SEP> 76.0 <SEP> 75.9 <SEP> 10.2 <SEP> 10.4 <SEP> 1736
 <tb> 29 <SEP> 6 <SEP> - <SEP> (CH2) <SEP> 4- <SEP> 54-57 <SEP> 76.4 <SEP> 76.5 <SEP> 10.3 <SEP> 10.6 <SEP> 1735
 <tb> 30 <SEP> 6- <SEP> (CH2) a - 77, <SEP> 1 <SEP> 77, <SEP> 1 <SEP> 10.6 <SEP> 10.6 <SEP> 1735
 <tb>
 
 EMI50.4
 TABLE 5 Melting points,

   IR compositions and data for compounds # 31 to 34
 EMI50.5
 OH OH (CHCRl R'yC (CH 1 Type of compound 9 9 Y "0 o (CH2) n-0-C- (CH2) r S- (CH2) p C-0- (CH2) n c- (CH2 ) i- CO- (CH
 EMI50.6
 
 <tb>
 <tb> Comp. <SEP> n <SEP> Rl <SEP> j <SEP> COMPOSITION <SEP> IR: 1 / #
 <tb> nO <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>: <SEP> S <SEP>% <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> 0
 <tb> calc. <SEP> found <SEP> calc. <SEP> found <SEP> calc. <SEP> found <SEP> [cm-1]
 <tb> 31 <SEP> 4 <SEP> CH3 <SEP> 2 <SEP> 70.3 <SEP> 70.5 <SEP> 8.9 <SEP> 9, <SEP> 0 <SEP> 5.2 <SEP> 5.4 <SEP> 1731
 <tb> 32 <SEP> 6 <SEP> CH3 <SEP> 2 <SEP> 71.6 <SEP> 71.5 <SEP> 9.3 <SEP> 9.5 <SEP> 4.8 <SEP> 4.9 <SEP> 1732
 <tb> 33 <SEP> 5 <SEP> C <SEP> (CH3) <SEP> 3 <SEP> 2 <SEP> 72.7 <SEP> 72.6 <SEP> 9.7 <SEP> 9.7 <SEP> 4.4 <SEP> 4.7 <SEP> 1736
 <tb> 34 <SEP> 5 <SEP> C <SEP> (CH3) <SEP> 3 <SEP> 1 <SEP> 72.1 <SEP> 72.0 <SEP> 9.5 <SEP> 9.6 <SEP> 4.6 <SEP> 4.7 <SEP> 1734
 <tb>
 

  <Desc / Clms Page number 51>

 EXAMPLE 35
Example 23 is repeated, with the difference that instead of the product of Example 1b, one starts from 6- (3, 5-ditert-butyl-4-hydroxyphenyl) -hexanol.

   The product (compound 35) corresponding to the formula:
 EMI51.1
 shows an IR absorption of the carbonyl band at 1723 cm- '. Composition: wedge. 77.6% C, 9.5% H, found 77.1% C, 9.5% H.



  EXAMPLE 36
In a round bottom flask fitted with a distillation column, 7.57 g (30 mmol) of methyl ester of trimellitic acid, 33 g (117 mmol) of the product of Example Ib and 0 are mixed, 45 g (1.8 mmol) of dibutyltin oxide. The mixture is heated to 180 ° C., while removing the methanol by distillation. After 2 hours, the pressure on the mixture is lowered to 533 hPa (= 400 torr), the temperature is then maintained at 180 ° C. for an additional 4 hours. The excess of 6- (3-tert-butyl-5-methyl-4-hydroxyphenyl) - hexanol is then removed by distillation (150 ° C., 4 Pa) and the crude product obtained is purified by chromatography (SiO2; first hexane, then hexane / ethyl acetate = 19/1).

   We obtain
24.7 g (87%) of a product corresponding to the formula:

  <Desc / Clms Page number 52>

 
 EMI52.1
 (Compound # 36); IR absorption of the carbonyl band at 1722 cm- '. Composition: calc. 75.9% C, 8.9% H, found 75.3% C, 9.3% H.



  EXAMPLE 37
16.5 g (70 mmol) of 4- (3tert-butyl-5-methyl-4-hydroxyphenyl) -butanol, 18.05 g (91 mmol) are introduced into a round bottom flask fitted with a distillation column ) methyl ester of 10-undecenoic acid and 80 mg (1.4 mmol) of dibutyltin oxide.



   The mixture is heated to 180 ° C., while removing the methanol by distillation. After 2 hours, the pressure on the mixture is lowered to 400 torr, then the temperature is maintained 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 (SiO2; hexane / ethyl acetate = 9/1).



   23.15 g (82%) of a product corresponding to the formula are obtained:

  <Desc / Clms Page number 53>

 
 EMI53.1
 Composition and IR data: see Table 6.



  EXAMPLES 38 TO 42
Compounds 38 to 42 are prepared in a manner analogous to the process described in Example 1. The data concerning the composition and the IR of compounds 38 to 40 appear in Table 6, the corresponding data of compounds 40 and 41 in Table 7.



   TABLE 6
Composition and IR data for compounds 37 to 40
 EMI53.2
 OH (CH3) 3CJ, CH3 Type of compound: j n 0. 1 a Il (CHO-ë - A
 EMI53.3
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> COMPOSITION <SEP> IR <SEP>: <SEP> 1 / A.
 <tb> n <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>:

    <SEP> C <SEP> = <SEP> 0
 <tb> calc. <SEP> found <SEP> calc. <SEP> found <SEP> [cm-1]
 <tb> 37 <SEP> 4 <SEP> - <SEP> (CH2) <SEP> a-CH = CH2 <SEP> 77.56 <SEP> 77.59 <SEP> 10.52 <SEP> 10.58 <SEP> 1719/1735
 <tb> 38 <SEP> 4-C <SEP> (CH3) <SEP> = CH2 <SEP> 74.96 <SEP> 74, <SEP> 95 <SEP> 9.27 <SEP> 9.48 <SEP> 1705
 <tb> 39 <SEP> 6-CH = CH2 <SEP> 75.43 <SEP> 75.20 <SEP> 9.50 <SEP> 9.53 <SEP> 1712/1725
 <tb> 40 <SEP> 6-C <SEP> (CH3) <SEP> = CH2 <SEP> 75, <SEP> 86 <SEP> 75.83 <SEP> 9, <SEP> 70 <SEP> 10, <SEP> 16 <SEP> 1705/1718
 <tb>
 

  <Desc / Clms Page number 54>

 
TABLE 7 Composition and IR data
 EMI54.1
 for compounds n 41 to 42
 EMI54.2
 OH (CH3) 3CJ.

   C (CH3) 3 Type of compound: L dd 0 Il (CHn-O-ë - A
 EMI54.3
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> COMPOSITION <SEP> IR <SEP>: <SEP> 1 / #
 <tb> nO <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>: <SEP> C <SEP> = <SEP> 0
 <tb> wedge. <SEP> found <SEP> wedge. <SEP> found <SEP> [cm-1]
 <tb> 41 <SEP> 6-CH = CH2 <SEP> 76.61 <SEP> 76.44 <SEP> 10.06 <SEP> 10.08 <SEP> 1725
 <tb> 42 <SEP> 6-C <SEP> (CH3) <SEP> = CH2 <SEP> 76.96 <SEP> 76, <SEP> 85 <SEP> 10.23 <SEP> 10.16 <SEP> 1719
 <tb>
 EXAMPLES 43 TO 45
Compound # 43 is prepared by the method described in Example 1. Compound # 44 is prepared by the method described in Example # 37; Compound No. 45 is prepared by the process described in Example No. 23.

   The data concerning the composition and the IR of the compounds Nos 43 to 45 are shown in Table 8.



   TABLE 8
Composition and IR data
 EMI54.4
 for compounds n 43 to 45
 EMI54.5
 OH OH (CHCJCH, CH ,. JC (CH,), Type of compost: 0 h- (CH2) - -ë - A - ë-0- (CH2) n
 EMI54.6
 
 <tb>
 <tb> Comp. <SEP> n <SEP> A <SEP> COMPOSITION <SEP> IR: 1 / #
 <tb> n <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>: <SEP> C <SEP> = <SEP> 0
 <tb> calc. <SEP> found <SEP> calc. <SEP> found <SEP> [cm-1]
 <tb> 43 <SEP> 4-CH2-CH2-73, <SEP> 61 <SEP> 73.14 <SEP> 9.08 <SEP> 9.21 <SEP> 1722
 <tb> 44 <SEP> 4 <SEP> - (CH2) 2-O- (CH2) 2- <SEP> 72, <SEP> 21 <SEP> 71.93 <SEP> 9.09 <SEP> 9.20 <SEP> 1728
 <tb> 45 <SEP> 6 <SEP> 72, <SEP> 25 <SEP> 72.41 <SEP> 8.49 <SEP> 8.53 <SEP> 1717
 <tb> # <SEP> S <SEP>%:

    <SEP> calc. <SEP> 4.82 <SEP> found <SEP> 4.69
 <tb>
 

  <Desc / Clms Page number 55>

 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 (manufacturer BASF; consisting of 25-35% succinic acid, 37-47% glutaric acid and 25-30% adipic acid ) in 450 ml of methanol, 22 ml (0.41 mole) of concentrated sulfuric acid are added dropwise at 10 ° C. The solution obtained is kept at reflux temperature for 3 hours. After cooling to 20-25 C, the mixture is neutralized with
55 g of potassium carbonate, it is poured over water and it is extracted with ethyl acetate. Evaporation of the solvent provides 23 g (36%) of the desired ester mixture as a slightly yellowish oil.



   Analysis by gas chromatography of the mixture of compounds corresponding to the formula: H3C-OCO- (CH2> x-COO-CH3 x = 2 23 moles% x = 3 44 moles% x = 4 33 moles% b) Preparation of the compound # 46
30.7 g (130 mmol) of 4- (3- tert-butyl-5-methyl-4-hydroxyphenyl) -butanol, 8.01 g ( 50 mmol) of the mixture of diesters described in a) and 490 mg (2 mmol) of dibutyltin oxide.



   The mixture is heated to 180 ° C., while removing the methanol by distillation. The mixture is kept at
 EMI55.1
 180 C for 15 additional hours. After cooling to 20-25 C, the crude mixture is purified by chromatography (SiO2; hexane / ethyl acetate 40: 1-> 19: 1-> 9: 1).



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

  <Desc / Clms Page number 56>

 



   Composition and IR data: see table 9.



  EXAMPLES 47 TO 51
The preparation of compounds Nos 47 and 48 was carried out using the corresponding phenolic alcohols by the process described in Example 46.



   For the preparation of compounds n 49, 50 and 51, we first prepared by synthesis, from Poly-THF-
 EMI56.1
 Dipropionsure 350 (manufacturer: Bayer AG, Leverkusen), the corresponding methyl ester by the method described in Example 46. The methyl ester of dicarboxylic acid of high molecular weight obtained is then transformed into the end products indicated using phenolic alcohols suitable by the process 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 next page)

  <Desc / Clms Page number 57>

 
TABLE 9
Composition and IR data for compounds 46 to 51 Type of compound (mixtures of diesters and oligomers)
 EMI57.1
 
 EMI57.2
 
 <tb>
 <tb> Comp. <SEP> Rl <SEP> n <SEP> A <SEP> COMPOSITION <SEP> IR <SEP> "1 / #
 <tb> n <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>: <SEP> C <SEP> = <SEP> 0
 <tb> wedge. <SEP> found <SEP> wedge. <SEP> found <SEP> [cm-l]
 <tb> in <SEP> which
 <tb> 46 <SEP> Me <SEP> 4 <SEP> x <SEP> = <SEP> 2 <SEP> 20-25 <SEP>% <SEP> 73.91 * <SEP> 73.79 <SEP> 9.22 <SEP> 9.37 <SEP> 1719
 <tb> - (CH2) x- <SEP> x <SEP> = <SEP> 3 <SEP> 40-43 <SEP>% <SEP> 75.43 * <SEP> 75.05 <SEP> 9.88 * <SEP> 9.98 <SEP> 1735
 <tb> 47 <SEP> t-Bu <SEP> 4 <SEP> x <SEP> = <SEP> 4 <SEP> 34-38 <SEP>%
 <tb> 48 <SEP> Me <SEP> 6 <SEP> 21% <SEP> x = 2 <SEP>; <SEP> 42% <SEP> x = 3 <SEP>;

    <SEP> 37% <SEP> x = 4 <SEP> 74.96 * <SEP> 74.91 <SEP> 9.68 * <SEP> 9.81 <SEP> 1720
 <tb> 49 <SEP> Me <SEP> 4 <SEP> F <SEP>: <SEP> 79-93 <SEP> OC <SEP> 70, <SEP> 26 <SEP> 69, <SEP> 92 <SEP> 9, <SEP> 61 <SEP> 9, <SEP> 78 <SEP> 1735
 <tb> 50 <SEP> t-Bu <SEP> 4 <SEP> (CH2 # 2-O # (CH2) 4-O] y- (CH2) 2- <SEP> 71.67 <SEP> 71.92 <SEP> 9.95 <SEP> 10.21 <SEP> 1737
 <tb> 51 <SEP> Me <SEP> 6 <SEP> y <SEP> = <SEP> 2.6 <SEP> 71, <SEP> 70 <SEP> 71, <SEP> 18 <SEP> 9, <SEP> 96 <SEP> 9, <SEP> 97 <SEP> 1736
 <tb>
 Me = methyl; t-Bu = tert-butyl * Composition calculated for x = 3 EXAMPLE 52 a) Preparation of the methyl ester of nitrilo-triacetic acid
74.8 ml (137.7 g) (1.4 mole) are added dropwise to a suspension of 100 g (0.52 mole) of nitrilotriacetic acid in 200 ml of methanol, at approximately 10 ° C. concentrated sulfuric acid.



   The mixture is kept for 22 hours at reflux temperature. After cooling to room temperature, the mixture is neutralized by carefully adding 150 g of potassium carbonate, it is poured over water and it is extracted with ethyl acetate.

  <Desc / Clms Page number 58>

 



   Evaporation of the solvent and drying of the residue under vacuum provides 57 g (47%) of methyl ester of nitrilotriacetic acid in the form of a colorless oil.



  IR (film on a KBr crystal): absorption of carbonyl at 1751 cm-i Composition: calculated 46.35% of C 6.48% of H 6.0% of N found 46.47% of C 6.53% of H 6.14% of N b) Preparation of compound n 52
1.76 g (7.5 mmol) of nitrilotriacetic acid methyl ester, 7 g (29.4 mmol) of 4- (3-) are introduced into a round bottom flask fitted with a distillation column. tert-butyl-5-methyl-4-hydroxyphenyl) -butanol and 25 mg (0.45 mmol) of dibutyltin oxide. The mixture is heated to 180 ° C., while removing the methanol by distillation. After 3 hours, the pressure is lowered to 400 torr and the temperature is maintained at 180 C for an additional 2 hours.



   The excess 4- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -butanol is then removed by distillation (150 C / 0.4 Pa) and the crude product obtained (SiO2; hexane) is purified by chromatography. / ethyl acetate 9: z 3: 1).



   5.6 g (88%) of a product corresponding to the formula are obtained:
 EMI58.1
 

  <Desc / Clms Page number 59>

 
Composition and IR data: see Table 10.



  EXAMPLES 53 TO 55
The preparation of compounds 53 and 55 is carried out by the process described in Example 52. The composition and IR data of the compounds are collated in Table 10.
 EMI59.1
 



  TABLE 10
 EMI59.2
 CH CH, OH JL R 3 s Type of compound: (CH) t 0 3
 EMI59.3
 
 <tb>
 <tb> Comp. <SEP> Rl <SEP> n <SEP> F <SEP> COMPOSITION <SEP> IR <SEP>: <SEP> 1 / Â.
 <tb> n <SEP> C <SEP>% <SEP>: <SEP> H <SEP>% <SEP>: <SEP> S <SEP>% <SEP>% <SEP>: <SEP> C <SEP> = <SEP> 0
 <tb> wedge. <SEP> found <SEP> wedge. <SEP> found <SEP> wedge.

    <SEP> found <SEP> [cm-l]
 <tb> 52 <SEP> Me <SEP> 4-72, <SEP> 39 <SEP> 72.39 <SEP> 8.93 <SEP> 8.83 <SEP> 1.66 <SEP> 1.48 <SEP> 1738
 <tb> 53 <SEP> t-Bu <SEP> 4-74, <SEP> 11 <SEP> 73.42 <SEP> 9.64 <SEP> 9.68 <SEP> 1.44 <SEP> 1.23 <SEP> 1747
 <tb> 54 <SEP> Me <SEP> 6 <SEP> - <SEP> 73, <SEP> 59 <SEP> 72.98 <SEP> 9.43 <SEP> 9.67 <SEP> 1.51 <SEP> 1.31 <SEP> 1739
 <tb> 55 <SEP> t-Bu <SEP> 6 <SEP> 75, <SEP> 03 <SEP> 74.18 <SEP> 10.02 <SEP> 10.28 <SEP> 1.33 <SEP> 1, <SEP> 33 <SEP> 1748
 <tb>
 EXAMPLES 56 TO 60
The preparation of compounds n 56 to 60 is carried out by the method described in Example 36. The composition and IR data of the compounds are collated in Table 11.



   (See table 11 next page)

  <Desc / Clms Page number 60>

 
 EMI60.1
 TABLE 11
 EMI60.2
 D-) OH CH CH3 OH CH3 1 3 Type of compound: (CH e (CH2) 0 0
 EMI60.3
 
 EMI60.4
 EXAMPLE 61 Preparation of 4- (3,5-dicyclohexyl-4-hydroxyphenyl) -hexanol
In a sulfonation flask, melt 258 g (1 mole) of 2,6-dicyclohexylphenol, 591 g (5 moles) of 1,6-hexanediol and heat them for 10 hours at 238 C with 36 g (0.64 mole) of potassium hydroxide. We acidify

  <Desc / Clms Page number 61>

 then slightly mix at 80 C with a 2M aqueous HCl solution. The phases are separated, the mineral phase is washed with toluene and the combined organic phases are concentrated on a rotary evaporator.

   Excess 1,6-hexane diol and 2,6dicyclohexylphenol unreacted are removed by distillation.



   The crystallization of the residue on a gasoline with a defined boiling limit (80-110 OC) provides 163 g (45%) of a product corresponding to the formula:
 EMI61.1
 OH oe 1)) OH j 1 F = 96 OC OH Composition: calculated 80.39% of C 10.68% of H found 78.62% of C 10.62% of H EXAMPLE 62
32.3 g (90 mmol) of 4- (3, 5-dicyclohexyl-4-hydroxyphenyl) -hexanol are transformed using 9.2 g (50 mmol) of adipic acid dichloride, by the method described in 'Example le, in 18.7 g (47%) of a product corresponding to the formula:
 EMI61.2
 

  <Desc / Clms Page number 62>

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



  IR (film on crystal of KBr): 1736.1717 cm-i (C = 0) Composition: calculated 77.76% of C 10.29% of H found 77.62% of C 10.05% of H EXAMPLES D '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, then they are 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, from which strips 1 cm wide and 10 cm long are cut. For comparison, another sample is prepared without stabilizers. Several of these strips of each plate are suspended in an air circulation oven heated to 135 ° C. or 149 ° C., and they are examined at regular intervals. The decomposition by oxidation of these bands is manifested by a yellow coloring beginning in the shape of a circle. A measure for the stability of the sample is the time in days until decomposition.



   (See table 12 on next page)

  <Desc / Clms Page number 63>

 
TABLE 12 Duration (in days) until the decomposition of the samples containing the combination of stabilizers 0.3% of DSTDP + 0.1% of compound of the invention or no stabilizer
 EMI63.1
 
 <tb>
 <tb> Number <SEP> from <SEP> days <SEP> from <SEP> aging <SEP> to
 <tb> Stabilizers <SEP> the oven <SEP> up to <SEP> decomposition
 <tb> to <SEP> 135 <SEP> OC <SEP> to <SEP> 149 <SEP> OC
 <tb> None <SEP> 1 <SEP> < <SEP> 1
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 8 <SEP> 126 <SEP> 50
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 13 <SEP> 115 <SEP> 40
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 17 <SEP> 156 <SEP> 65
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 20 <SEP> 162 <SEP> 60
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 21 <SEP> 175 <SEP> 38
 <tb> DSTDP <SEP> + <SEP> compound

   <SEP> n <SEP> 22 <SEP> 247 <SEP> 57
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 23 <SEP> 245 <SEP> 85
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 24 <SEP> 140 <SEP> 43
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 25 <SEP> 121 <SEP> 24
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 26 <SEP> 151 <SEP> 33
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 28 <SEP> 147 <SEP> 47
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 29 <SEP> 145 <SEP> 49
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 30 <SEP> 194 <SEP> 50
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 35 <SEP> 148 <SEP> 50
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 36 <SEP> 190 <SEP> 71
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 52 <SEP> 158 <SEP> 55
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 53 <SEP> 158 <SEP> 48
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 54 <SEP> 161 <SEP> 55
 <tb>

  DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 55 <SEP> 150 <SEP> 43
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 56 <SEP> 170 <SEP> 52
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 57 <SEP> 193 <SEP> 70
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 58 <SEP> 173 <SEP> 52
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 59 <SEP> 163 <SEP> 63
 <tb> DSTDP <SEP> + <SEP> compound <SEP> n <SEP> 60 <SEP> 159 <SEP> 48
 <tb>
 EXAMPLE 64 Stabilization of an Acrylonitrile-Butadiene-Styrene Terpolymer (ABS)
The stabilizers indicated in Table 13 are dissolved in 40 ml of a mixture of hexane and isopropanol. The solution is poured with vigorous stirring into a dispersion of 100 g of ABS in 600 ml of water, after which the

  <Desc / Clms Page number 64>

 solution is completely absorbed by ABS in about one minute.

   The polymer powder containing the stabilizers is then filtered and dried under vacuum at 40 ° C. for 40 hours.



   The other stages of transformation are also carried out for comparison purposes with a sample without stabilizers.



   To the dried powder, 2% of titanium dioxide is added as pigment and 1% of ethylene bisstearamide as a lubricant. The mixture is then mixed over a period of
 EMI64.1
 4 minutes on a two-cylinder mill at 180 C.



  From a kneaded sheet, a 0.8 mm thick plate is pressed at 175 ° C. from which 45 x 17 mm2 test pieces are cut. The effectiveness of the added stabilizers is tested by thermal aging in an air circulation oven at 180 C. As a criterion, the appearance of color is used after 45 minutes. The intensity of the color is determined by ASTM D 1925-70 (degree of yellow). The test results are collated in Table 13. The highest figures correspond to the most intense yellow coloration. The tests show that the yellow coloration is effectively repressed by the compounds according to the invention.



  (See table 13 next page)

  <Desc / Clms Page number 65>

 
TABLE 13 Degree of yellow after 45 minutes of aging in an oven of samples not containing stabilizers, containing 0.5% of dilauryl thiodipropionate (DLTDP) and 0.5% of DLTDP + 0.25% of the conforming compound to the invention indicated
 EMI65.1
 
 <tb>
 <tb> Stabilizers <SEP> Degree <SEP> from <SEP> yellow
 <tb> at <SEP> end <SEP> from <SEP> 45 <SEP> mn <SEP> to <SEP> 180 <SEP> Oc
 <tb> None <SEP> 78
 <tb> DLTDP <SEP> 75
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 1 <SEP> 26
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 7 <SEP> 25
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 8 <SEP> 26
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 12 <SEP> 34
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 13 <SEP> 39
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 15 <SEP> 33
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO

   <SEP> 16 <SEP> 34
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 17 <SEP> 26
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 19 <SEP> 31
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 20 <SEP> 26
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 21 <SEP> 33
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 22 <SEP> 21
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 23 <SEP> 29
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 24 <SEP> 32
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 25 <SEP> 41
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 26 <SEP> 28
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 28 <SEP> 30
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 29 <SEP> 32
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 31 <SEP> 29
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 32 <SEP> 27
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 33 <SEP> 32
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 34 <SEP> 30
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 39

   <SEP> 36
 <tb> DLTDP <SEP> + compound <SEP> no <SEP> 40 <SEP> 26
 <tb> DLTDP <SEP> + <SEP> compound <SEP> nO <SEP> 42 <SEP> 32
 <tb>
 

  <Desc / Clms Page number 66>

 EXAMPLE 65 Stabilization of X-SBR Latex (Carboxylated SBR Latex)
Each time 0.25 parts by weight of the compounds according to the invention indicated in table 14 are dissolved in a little methanol and they are diluted in 100 parts by weight of X-SBR latex (styrene butadiene copolymer). An exactly defined quantity of latex is then introduced into Petri dishes and dried in a dryer at 80 C. Transparent films with a layer thickness of approximately 0.2 mm are obtained. For comparison, a sample without stabilizers is prepared.



   The efficiency of the stabilizers indicated is tested by thermal aging in an oven with air circulation at 135 C. After the time intervals indicated in table 14, the coloration of the samples is determined according to ASTM D 1925-70 (degree of yellow). The test results are collated in Table 14. The highest figures correspond to the most intense yellow coloration. The tests show that the yellow coloration is effectively repressed by the compounds according to the invention.



   TABLE 14
Degree of yellow at the end of the aging period indicated at 135 OC
 EMI66.1
 
 <tb>
 <tb> Degree <SEP> from <SEP> yellow
 <tb> Stabilizer <SEP> after <SEP> a <SEP> duration <SEP> from <SEP> aging <SEP> from
 <tb> 4 <SEP> h <SEP> 12 <SEP> h <SEP> 24 <SEP> h <SEP> 40 <SEP> h
 <tb> None <SEP> 92 <SEP> * <SEP> * <SEP> *
 <tb> 0.25 <SEP>% <SEP> from <SEP> compound <SEP> n <SEP> 31 <SEP> 46 <SEP> 52 <SEP> 64 <SEP> 75
 <tb> 0, <SEP> 25 <SEP>% <SEP> from <SEP> compound <SEP> n "32 <SEP> 40 <SEP> 46 <SEP> 58 <SEP> 69
 <tb>
 * not measurable (black sample)


    

Claims (19)

 CLAIMS 1. Compound corresponding to formula I:  EMI67.1  in which n denotes an integer between 4 and 8 and m denotes an integer between 1 and 4; A, in the case where m is equal to 1, represents a group  EMI67.2  C1-C25 alkyl, which is unsubstituted or substituted by a Cg-Cg cycloalkyl group; or it represents a C-Cs alkyl group, which is interrupted by a Cg-Cg cycloalkyl group or by one or more of the groups -S -, - O- and / or-NR2-; or, in the case where m is equal to 1, A denotes a C5-C8 cycloalkyl group which is unsubstituted or substituted by a C1-Cl2 alkyl or C-C12 alkenyl group; a C6-C8 cycloalkenyl group which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group;  a phenyl group, which is unsubstituted or substituted by a C1-C2 alkyl or C2-C12 alkenyl group; a naphthyl group, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; a biphenyl group, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; or a C2-C25 alkenyl group; a C6-C10 bicycloalkenyl group; a C7-C12 phenylalkyl group; a Cg-C phenylalkenyl group; a Cn-Cg naphthylalkyl group; a C12-Cl6 naphthylalkenyl group; a C 13 -C 18 biphenylalkyl group; a biphenylalkenyl group in C14-C18; or a group corresponding to formula II:    <Desc / Clms Page number 68>    EMI68.1  in the case where m is equal to 2, A denotes a direct bond; a C1-Cl2 alkylene group; C2-C12 alkenylene Cg-Cg cycloalkylene, which is unsubstituted or substituted by a C1-C12 alkyl or C-Cis alkenyl group; a C6-C8 cycloalkenylene group, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; ; a C6-Cio 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-; or A, in the case where m is equal to 2, denotes a C2-C36 alkylene group interrupted by a C-C6 or phenylene cycloalkylene group or at least one of the groups -S-, -O- or -NR2- ; A, in the case where m is equal to 3, denotes a (C1-C8 alkane) triyl group; a (C2-CS alkene) triyl group; a benzenetriyl group; a group  EMI68.2  naphthalenetriyl;  a trivalent group responding to the  EMI68.3  RS formula-R-M-R? - or a group (C2-C18 alkane)  EMI68.4  triyle, which is interrupted by at least one of the groups -S -, - 0- or-NR2-; A, in the case where m is equal to 4, denotes a benzene radical; naphthyl; tetrahydrofuryl or cyclohexyl having 4 free valences; R1 and R1 'represent, independently of each other, a C1-C24 alkyl or C5-C8 cycloalkyl group; R2 represents H or a C1-C4 alkyl group; R3 and R4 independently of one another denote a C1-C4 alkyl group; and  <Desc / Clms Page number 69>    R, R6 and R7 independently of one another represent a C1-C3 alkylene group; on the condition of  EMI69.1  when n = 4;  R1 represents a methyl or cyclohexyl group and R1 represents a methyl, tert-butyl or cyclohexyl group, and with the additional condition that when A contains an ethylenic double bond R1 is a methyl group and R1 'is a tert-butyl group. 2. Compound corresponding to formula I according to  EMI69.2  claim 1, wherein RI denotes a secondary or tertiary C3-C24 alkyl or C1-cog cycloalkyl; and RI denotes a C1-C10 alkyl or a C5-C8 cycloalkyl group. 3. Compound corresponding to formula I according to  EMI69.3  claim 1, wherein RI denotes a tert-butyl group and RI denotes a methyl group. 4. Compound corresponding to formula Ia  EMI69.4  in which n is an integer between 4 and 8 and m is an integer between 1 and 3;  A, in the case where m is equal to 1, represents a group  EMI69.5  C1-C25 alkyl, which is unsubstituted or substituted by a Cg-Cg cycloalkyl group, or else it represents a C-Cs alkyl group, which is interrupted by a C5-CS cycloalkyl group or by one or more of -S-, -0- and / or -NR2¯ groups; or A, when m is 1, denotes a C1-Cog cycloalkyl group which is unsubstituted or substituted by a C1-C2 alkyl or C2-C12 alkenyl group; a Cg-Cg cycloalkenyl group which  <Desc / Clms Page number 70>  is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group; phenyl, which is unsubstituted or substituted by a C1-C12 alkyl or C2-C12 alkenyl group;  naphthyl, which is unsubstituted or substituted by a C1-Cl2 alkyl or C2-C12i biphenyl alkenyl group, which is unsubstituted or substituted by a C1-Cl2 alkyl or C2-C12 alkenyl group; or C2-C25 alkenyl; C6-C10 bicycloalkenyl;  EMI70.1  phenylalkyl C'y-C phenylalkenyl C-y-Ci naphthylalkyl C-Cg; C1-C16 naphthylalkenyl; C-C8 biphenylalkyl; C-Cg biphenylalkenyl or a group corresponding to formula II:    EMI70.2  A, when m is equal to 2, denotes a direct bond, a C1-C1 alkylene group C2-C12 alkenylene, cycloalkylene Cg-Cg, which is unsubstituted or substituted by a C1-C12 alkyl or alkenyl group C2-C12, Cg-Cg cycloalkenylene, which is unsubstituted  EMI70.3  or substituted by a C1-C1 alkyl group or C1-C4 alkenyl C8-cycloalkenylene phenylene, naphthylene, or C2-C1S alkylene interrupted by a C1-Cg cycloalkylene group or phenylene or by at least one of -S-, -O- or -NR2- groups;  A, when m is equal to 3, denotes a (C1-CS alkane) triyl group ((C2-CS alkene) triyl, benzenetriyl,  EMI70.4  naphthalenetriyl; a trivalent group responding to the  EMI70.5  R6 1 formula-R-N-R-or a group (C2-C1S alkane)  EMI70.6  triyle, which is interrupted by at least one of the groups - S -, - 0-or-NR2-; R1 represents a methyl or tert-butyl group;  <Desc / Clms Page number 71>  R2 represents an H atom or a C1-C4 alkyl group; R3 and R4 independently of one another denote a C1-C4 alkyl group; and  EMI71.1  RS, R6 and R7 independently of one another represent a C1-C3 alkylene group; with the proviso that, when n = 4 or when A contains an ethylenic double bond, R1 is a methyl group. 5. A compound corresponding to formula I according to claim 1, in which A, in the case where m is equal to 1, represents a C2-C2S alkyl group which is unsubstituted or substituted by a CS-Cg cycloalkyl group, or it represents a C2-C25 alkyl group which is interrupted by a C5-C8 cycloalkyl group or by one or more of the groups -S-, -O- and / or -NR2-; or A, when m is equal to 1, denotes a C5-C8 cycloalkyl group which is unsubstituted or substituted by a C1-C12 alkyl group a Cg-Cg cycloalkenyl group which is unsubstituted or substituted by a  EMI71.2  C1-C1 alkyl group; a phenyl group, which is unsubstituted or substituted by a C1-C6 alkyl group or a C2-C25 alkenyl group; a C7-C12 phenylalkyl group; ;  or a group corresponding to formula II:  EMI71.3  A, when m is equal to 2, denotes a direct bond,  EMI71.4  a CC alkylene group, C2-C12 alkenylene, Cg-Cg cycloalkylene, which is unsubstituted or substituted by a C1-C12 alkyl group, a Cg-Cg cycloalkenylene group, which is unsubstituted or substituted by a group C1-C12 alkyl; a phenylene 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-; or  <Desc / Clms Page number 72>    EMI72.1  A, when m is equal to 2, denotes a C2-C1S alkylene group interrupted by a C1-Cog or phenylene cycloalkylene group, or by at least one of the groups -S-, -0- or -NR2-; and A, when m is equal to 3, denotes a (C1-C8 alkane) triyl, (C2-CS alkene) triyl, benzenetriyl group; a trivalent group responding to the  EMI72.2  RGReformule-RS-N-P-; or a group (C2- alkane  EMI72.3  Cig) triyl, which is interrupted by at least one of the groups -S-, -O- or -NR2-;  and A, when m is equal to 4, denotes a benzene or cyclohexyl radical having 4 free valences. 6. A compound corresponding to formula I according to claim 1, in which R1 ′ denotes a tert-butyl or cyclohexyl group and R1 denotes a methyl, tert-butyl or cyclohexyl group; n is a number between 4 and 6; and A, when m is equal to 1, represents a C6-C18 alkyl or C2-C12 alkenyl group; A, when m is equal to 2, represents a bond  EMI72.4  direct; a C1-C12 alkylene group; a group  EMI72.5  phenylene; ; S  EMI72.6  or a C2-C36 alkylene group interrupted by 1 to 5 oxygen or sulfur atoms; A, when m is equal to 3, denotes a group  EMI72.7  benzenetriyl or a trivalent group corresponding to the  EMI72.8  CH2- 1 formula-CH-N-CH; and  EMI72.9  A, when m is equal to 4, denotes a benzene radical having 4 free valences.  <Desc / Clms Page number 73>   7. Compound corresponding to formula I according to claim 1, in which n denotes an integer between 5 and 8. 8. Compound corresponding to formula I according to claim 1, in which n denotes an integer between 6 and 8. 9. Compound corresponding to formula I according to claim 6, in which m is 1 or 2. 10. Compound corresponding to formula I according to  EMI73.1  claim 9, corresponding to the formula:  EMI73.2    EMI73.3  in which A denotes - (CH2) j-; - (CH2) k-S- (CH2) k-;  EMI73.4    EMI73.5  or- (CH2) 2-0- [(CH2) 2-0-] j- (CH2) 2-; j is 0 or an integer between 1 and 4; and K denotes an integer between 1 and 3. 11. One of the compounds a) to 1) a) 6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl stearate;  EMI73.6  b) 6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl stearate; c) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyD-hexyl] succinate; d) bis- [6- (3-tert-butyl-4-hydroxy-) adipate 5-methylphenyl) -hexyl];  <Desc / Clms Page number 74>  e) bis- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] suberate; f) bis- [6- (3,5-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] isophthalate; g) bis- [6- (3,5-di-tert-butyl-4-hydroxyphenyD-hexyl] isophthalate;    h) tris trimellitate [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl]; j) tris- [6- (3,5-di-tert-butyl-4hydroxyphenyl) -hexyl] trimellitate; k) tris- [6- (3-tert-butyl-4-hydroxy-5-methylphenyl) -hexyl] trimesinate; 1) the tris- [6- (3,5-di-tert-butyl-4-hydroxyphenyl) -hexyl] trimesinate according to claim 1. 12. Composition containing an organic material sensitive to thermal, oxidizing and / or actinic degradation and at least one compound corresponding to formula I according to claim 1.  13. Composition according to claim 12, in which the organic material is a synthetic organic polymer or a mixture of these polymers.  14. Composition according to claim 13, in which the synthetic organic polymer is a polyolefin or a copolymer of styrene.  15. Use of compounds corresponding to formula I according to claim 1 for the stabilization of an organic matter with respect to thermal, oxidative and / or actinic degradation.  16. Use of compounds corresponding to formula I according to claim 15 as antioxidants in synthetic organic polymers.  <Desc / Clms Page number 75>   17. Process for the stabilization of an organic material with respect to thermal, oxidative and / or actinic degradation, characterized in that at least one compound corresponding to formula I is added to this material.   18. Composition containing an organic material sensitive to thermal, oxidative and / or actinic degradation and at least one compound corresponding to formula IV  EMI75.1  in which n is an integer between 4 and 8 and R1 represents a methyl group and R1 represents a tert-butyl group. 19. Use of compounds corresponding to formula IV according to claim 18 for the stabilization of an organic material with respect to thermal, oxidative and / or actinic degradation.