CA2090082A1 - Carboxylic acid esters of hydroxyphenylalkanols as stabilisers - Google Patents

Abstract

Carboxylic acid esters of hydroxyphenylalkanols as stabilisers Abstract The novel compounds of the formula I

Description

2~g~82 _bpxYlic acid esters of hy~y~h~nols as stabilisers The present invention relates to novel carboxylic acid esters of (D-(3,5-dialkyl-4-hydroxyphenyl)alkanols, the organic materials stabilised against thermal, oxidative and actinic degradation using these compounds, the use of the novel compounds as stabilisers and novel Cd-(3,5 dialkyl-4-hydroxyphenyl)alkanols.

The use of the esters of ld-hydroxyphenyl-o~-carboxylic acid esters as stabilisers for organic n1aterials is known.

A number of publications relate to corresponding inverse esters: Chem. Abstr. 84 32016k, DE-A-2 147 544, EP-B-171 139, EP-A-349 380, NL-A-79-05000, GB-A-l 509 876, Chem. Abstr. 84 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 carboxylic acid esters of 3-(3,5-di~tert-butyl-4-hydroxyphenyl)alkan- l-ols, 3-~3-tert-butyl-5-methyl-4-hydroxyphenyl)alkan- l-ols and individual 4-(3,5-dialkyl-4-hydroxyphenyl)alkan-1-ols, as well as their use as polymer stabilisers.

Several novel carboxylic acid esters of ~-(3,5-dialkyl-4-hydroxyphenyl)alkanols have now been found which have par~icularly good stabiliser properties.

One subject of the present invention ~erefore comprises compounds of the formula I

OH
R1~

L (CH2) n --C ~;~ A

in which n is an integer from the range from 4 to 8 and m is an integer from the range from 2~99~2 I to4;
it` m = l, A is Cl-C2salkyl, whicll is llnsllbstilllted or sllbs~itllte(l by C5-C8cycloalkyl; or is C2-C2salkyl which is intelrllpte(l by C5-C8cycloalkyl or one or more of the grollps -S-, -C)-nn-l/or -NR2-; or, ir m = ~ is Cs-C8cyclo~11kyl, which is unsllbstillltecl or sllbstitllted by Cl-CI2alkyl or C2-CI~llkenyl; C~,-Cxcycloalkellyl, whicll is ~Insllbslilllle(l or sllbstillltecl by Cl-CI2alkyl or C'2-CI2c~lkellyl; pllellyl, which is llnsllhstilllted or sllbstitllted by C`l-CI2alkyl or C2-CI2alkellyl; naphtllyl, which is llnsubstitlltecl or sllbstitllte(l by Cl-Cl2alkyl or C2-CI2alkenyl; biphenyl, which is llnsubstitllted or substituted by Cl-Cl2alkyl or C2-Cl~alkenyl; or C2-C2salkenyl; C6-CI0bicycloalkenyl;
C7-CI2phenylalkyl; C8-Cl2phenylalkenyl; Cll-Cl6naphthylalkyl; Cl2-Cl6naphthylalkenyl;
Cl3-CI8biphenylalkyl; Cl4-Cl8biphenylalkenyl; or a group of the formula Il - C~12 CH2~ OH (:lI);

if m = 2, A is a direct boncl; Cl-Cl2alkylene; C2-Cl2alkenylene; Cs-C8cycloalkylene, which is unsubstituted or substituted by Cl-Cl2alkyl or C2-Cl2alkenyl;
C6-C8cycloalkenylene, which is unsubstituted or substituted by Cl-Cl2alkyl or C2-CI2alkenyl; C6-Cl0bicycloalkenylene; phenylene; naphthylene; a divalent heterocyclic radical from the group comprising furan, thiophene or pyrrole, which is saturated on the nitrogen atorn by hydrogen or the substituent -R2; or, if m = 2, A is C2- C36alkylene which is interrupted by C5-C8cycloalkylene or phenylene or at least one of the groups -S-, -O- or -NR2-;
if m = 3, A is Cl-C8alkanetriyl; C2-Cgalkenetriyl; benzenetriyl; naphthalenetriyl; a trivalent group of the formula _ R5--N--R7_; or C2-Cl8aLkanetxiyl, which is intexrupted by at least one of the groups -S-, -O- or -NR2-;
or, if m = 4, A is a benzene radical, naphthyl radical, tetrahydrofuryl radical or cyclohexyl radical having 4 free valencies;
Rl and Rl, independently of one another, are Cl-C24alkyl or Cs-C8cycloaLkyl;
R2 is H or Cl-C4alkyl;
R3 and E~4, independently of one another, are Cl-C4alkyl; and Rs, R6 and R7, independently of one another, are Cl-C3alkylene.

Cl-C24Alkyl or Cs-C8cycloalkyl Rl and Rl axe for example, independently of one 20~0082 another, melhyl, ethyl, propyl, blllyl, pen~yl, hexyl, heplyl, oc~yl, nonyl, decyl, cyclopentyl, cyclohe~yl, cycloheptyl or eyclooctyl.

1~1 is preterllbly secoîldary or ~er~iary C3-C2~alkyl, t`or example 2-bll~yl (sec-bll~yl), ~ert-bll~yl, 2-1~ell~yl, 2-hexyl ol~ 3-he,Yyl, or Rl is Cs-C8cycloalkyl, for example cyclohexyl, an(l Rl is Cl-C'I(~alkyl or C~-Cgcycloalkyl.
Rl is par~iclllarly preler(~n~ially secondary or tertklry C3-Cl8alkyl or Cs-CBcycloalkyl, for example isopropyl, sec-blltyl, tert-blltyl or cyclohexyl, and Rl ;s C3-C8alkyl or Cs-C8cycloalkyl or is methyl.

Partieuku1y preferred compounds of the formula I are those in whieh Rl is methyl, tert-butyl or eyelohexyl, in partieular methyl, and Rl is tert-blltyl or eyelohexyl, in partieular tert-butyl.

C1-C4~lkyl R2, R3 und R'~ are methyl, ethyl, l-propyl (n-propyl), 2-propyl (isopropyl), l-butyl (n-blltyl), 2-blltyl (sec-butyl), 2-methylpropyl (isobutyl) or l,l-dimethylethyl (tert-butyl); methyl or tert-butyl is preferred.

Cl-C3Alkylene Rs, R6 and R7 are methylene, 1,1- or 1,2-ethylene, or l,1-, 1,2-, 2,2- or 1,3-propylene. Methylene is preferred.

If A is C1-C2salkyl, it is a branched or straight-ehain radieal, for example methyl, ethyl, propyl, isopropyl, n-butyl, see-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 methylpentyl, 1,3 dimethylbutyl, n-hexyl, l-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, l-methylheptyl, 3-methylheptyl, n-oetyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, deeyl, undecyl, 1-methylundecyl, dodeeyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradeeyl, pentadecyl, hexadecyl, heptadeeyl, oetadeeyl, eieosyl, doeosyl or pentaeosyl; straight-chain aLkyl is preferred and straight-chain C6-Cl8alkyl is particularly preferred.

As Cl-C2salkyl substituted by Cs-C8eyeloalkyl, A is, for example, eyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclohexylethyl, 2-eyelohexyl-n-propyl, 3-cyclohexyl-n-propyl or 4-cyclohexyl-n-butyl.

As C2-C2salkyl interrupted by Cs-CBcycloalkyl or one or more of the groups -S-, -O-and/or -NR2-, A is one of the alkyl radieals described above, with the exception of methyl, 2090~82 in the chain of which cyclopentylene or cyclopentylidene, cyclohexylene or cyclohexylidene, cycloheptylene or cycloheptylidene, cyclooctylene or cyclooctylidene is inserted at one point or the abovemetltiolled groups containing hetero atoms are inserted at one or more points. A thcrefore, for example, has the folmulae -C6~ll~C~I3 ,-c~l2-s-c4H9~-c2H4-o-c2H~l-o-cl2H~s~-cl8H36-N(c'~H9)2 As Cs-C8cycloalkyl or C6-C8cycloalkenyl which is unsubstituted or substituted byCl-CI~alkyl or C2-CI2alkenyl, A can be, for example: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, 2-cyclohexenyl, 3-cycloheptenyl, cyclooctatetraenyl or 4-tert-butylcyclohex-2-enyl. Cyclohexyl and cyclohexenyl, especially cyclohexyl, are preferred.

As phenyl, naphthyl or biphenyl substituted by Cl-Cl2alkyl or C2-CI2alkenyl, A is, inter alia, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, vinylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, methyl-di-t-butylphenyl, 1,1,3,3-tetramethylbutylphenyl and 1,1,3,3,5,5-hexamethylhexylphenyl, dodecenylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, l-ethylnaphthyl, 2-propylbiphenyl-4-yl or 4-(1-he~c-3-enyl)biphenyl-8-yl. Phenyl, which is unsubstitllted or substituted by 1-3, for example 1-2 and in particular 1 Cl-C4alkyl group(s), in particular methyl, is preferred.

C2-C2sAlkenyl A is, for example, vinyl, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta- 2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl or n-octadec-4-enyl.

C7-CI2Phenylalkyl, C7-CI2phenylalkenyl, Cll-CI6naphthylalkyl, Cll-Cl6naphthylalkenyl, Cl3-Cl8biphenylalkyl or Cl3-Cl8biphenylalkenyl A is Cl-C6alkyl or Cl-C6alkenyl substituted by phenyl, naphthyl or biphenyl, for example benzyl, phenethyl, 3-phenylpropyl, c~-methylbenzyl, a,a-dimethylbenzyl, 2-phenylethenyl, 1-phenylprop-2-enyl, 6-phenylhexyl, 1-naphthylmethyl, 2-naphthylmethyl, l-naphthyleth-1-yl, 2-(4-biphenylyl)prop-2-yl or 1-(4-biphenylyl)pent-3-en-1-yl.
C6-CIOBicycloalkenyl or C6-CIObicycloalkenylene A is an unsaturated bicyclic, monovalent or divalent radical of 6 to 10 carbon atoms which as a monovalent radical can 2~9Q0~2 be, for example, bicyclo[2.2.1]hepta-5-en-2-yl and as a divalent radical can have, for oxample, the folmulac ~ or ~\ .

I`lle divalent (for m - 2), trivalent (for m = 3) and tetrnvnlent radicnls A (for m = 4) are derived from the monovalent radicals mentioned above. A divalent radical differs from the corresponding monovalent radical ;n that it contains an open bond in place of a hydrogen atom and a trivalent radical differs from the corresponding monovalent radical in that it contains two open bonds in place of two hydrogen atoms; a tetravalent radical differs from the corresponding monovalent radical in that it contains three open bonds in place of three hydrogen atoms. Thus, within the fMmework of the indicated meanirlgs, for example, A, as a divalent radical, can also be methylene, ethylene, -CH2-C(CH3)2-CH2-, prop-2 enylidene, 1,3-propylene, 1,4-butylene, I,S-pentylene, 1,6-hexylene, o-, m- or p-phenylene, CH2~CH2-, CH2 CH2~CH2-CH2-, -C2H4-S-C2H4- OI' -C2H4-~O-C2H4-, as a trivalent radical can be, ~or example, -CH2-CH-CH2~

~3 or -CH2~ and as a trivalen~ radical can be, for example, or~--.

The novel esters of the forrnula I can be prepared by conventional esterification or transesterification methods from c~-hydroxyphenylalkanols of the formula IV
OH

R~ (IV~ and organic carboxylic acids of the forrmula V
~CH2)n OH

2090~8 r ol L~l - C ~ A (V) or derivatives ot` such carboxylic acids, t`or example by methods such as are described in Telrahedron 36, ~09 (1980). The symbols R~ , A, n and m in the fonnulac IV ancl V have the mennings indicated above ~or folTnula 1. Suitable carboxylic aci~l derivatives are, for example, anhydrides, chlorides or lower alkyl esters, for example methyl or ethyl esters. Suitllble esterification catalysts, such as mineral acids (for example sulfuric acid) or sulfonic acids (t`or example p-toluenesulfonic acid) can be used in the syntheses if appropriate.

The reaction can be cal~ied out in a manner known per se, expediently by adding one of the two educts to the second educt and mixing the two reactants thoroughly, preferably with the exclusion of oxygen. The reaction can be carried out in the presence of a solvent, for example toluene, or also without a solvent. The temperature control is not critical; the temperature can be between the melting point and the boiling point of the reaction mixture, for example between -50 and 10~C, preferably between 0 and S0CC. The purification of the resulting product can also be carried Ollt in accordance with known methods, for example by washing with water/HCI, extraction with an organic solvent, crystallisation and/or chromatography. Preferred solvents for the extraction and for the chromatographic purification step are hexane, ethyl acetate or mixtures thereof.
If the derivative of the carboxylic acid of the ~ormula V used in the reaction is the acid chloride, an acid acceptor is expediently added to the reaction mixture. Suitable acid acceptors are, for example, amines, such as pyridine or triethylamine. Preferably the amount of the acid acceptor is at least equivalent to the amount of the acid chloride and is, for example, 1 to 2 equivalents, in particular 1.2 to 1.7 equivalents, with respect to the acid chloride.

If the reaction is carried out as a transesteri~lcation of an alcohol of the formula IV with the ester of a carboxylic acid of the forrnula V, conventional transesterification catalysts are expediently added to the reaction mixture. Such catalysts are, for example, organic or inorganic bases (for example lithium amide, lithium methoxide, potassium hydroxide and the like) or Lewis acids (for example dibutyltin oxide).

If the carboxylic acid of the formula V and the alcohol of the formula IV aIe used directly as educts, the reaction is expediently carried out using a water separator, distilling off 209~082 water an(l/or ~Ising rc.lgen~s which abs()rb libcr(llc(l w~ltcr, ror cxalllple, dicyclohcxylcarho(liillli(tc.

'[`he use Or mi,~ lres ol` ~arboxylic aci(ls Or Ihe l`orm~lla V or tlleir der;vativcs can be of par~iCIIIar prac~ical illtel'CS~ ill thc prcpnrn~ioll Or compollnds of the formulll 1 Sucil mixlllros call be usc(l l`or the synthesis in the manner described above, correspollding mixtllres of compolln(ls of the formula I being oblaine(l. Mixtures of compolmds of the formula I can be use(l as sllch as stabilisers.

Alcohols of the formula IV are themselves also effective as stabilisers. Compositions containing (a) an organic material sensitive to oxidative, thermal and/or actinic degradation and (b) a compound of the formula IV, and also the use of compounds of the formula IV for stabilising organic material against o~idative, thermal or actinic degradation, are thereEore further subjects of the invention.

The compositions according to the invention pret`erably contain those compounds of the formula IV in which ~I has the meaning of seconclary or tertiary C3-C24alkyl or Cs-C8cycloalkyl, and Rl has the meaning Cl-CIOalkyl or C5-C8cycloalkyl. Particularly preferentially, Rl has the meaning of secondary or tertiary C3-CI8alkyl or Cs-C8cycloalkyl, for example isopropyl, sec-butyl, tert-butyl or cyclohexyl, and R1 is C3-C8alkyl or Cs-C8cycloalkyl or is methyl.

Compounds of the formula IV in which ~1 is methyl, tert-butyl or cyclohexyl, in particular methyl, and Rl is tert-butyl or cyclohexyl, in particular tert-butyl, are particularly preferred in the compositions according to the invention.

The compositions according to the invention preferably contain those compounds of the forrnula IV in which n is a number from the range 5 to 8, for example 6 to 8 and in particular the number 6.

The alcohols of the formula III described further below are also particularly preferred in the compositions according to the invention.

The cd-(hydroxyphenyl)alkanols of the formula IV can be prepared by known processes or analogously to such processes. Thus, the compounds of the formula IV are obtainable, for example, by the process described in US-A-4 260 832 or by a process analogous to this.

The correspondillg 2,6-disllbslitute(l phenols are then reac~ed wi~h o~,~-alkancliols in lhe presence of alkali mctal, alkali mctal hyd~ lcs or alkali metal alkoxidcs a~ ~empela~llres Or 20() to 300C wi~h rem()val of ~he wa~er rorll~ed dllring ~he reac~i()n.

Tllc l~ro(lllc~ e.ln lhell l~e isoklle(l by el)llvellli()n.ll me~ll()(l~s nll(l use(l for rcac~ioll with carhoxylic aci(l dcriv~llives ot` the l`orlnlllll V; h()wevcr, it is IlISO possible to use lhe crude prodllc~ direc~ly wi~h(~ furlller pllrificll~i()ll t`or ~he prepllrlltioll ol` compoullds of ~he ~ormulà [.

If a 2,6-disubs~ituted phenol in which none or at most one of the alkyl or cycloalkyl substituents is tèrt-butyl is used in place of the starting phenols described inUS-A-4 260 832, novel compolmds of the formula III

OH
G1~

(CH2)n OH

in which Gl and Gl have the meanings indicated further above for Rl and R1, but with the exception of tert-butyl for Gl, are obtained. As defined further above for formula I, n is an integer from the range 4 to 8.

A compound of the forrnula III is also a subject of the invention.

Preferred compounds of the formula III are those in which Gl has the meaning of secondary or tertiary C3-C24alkyl or C5-C8cycloalkyl; and Gl has the meaning Cl-ClOalkyl or Cs-C8cycloalkyl. G1 particularly preferentially has the meaning of secondary or tertiary C3-CI8alkyl or Cs-C8cycloalkyl, for example isopropyl, sec-butyl, tert-butyl or cyclohexyl, and G' is C3-C8alkyl with the exception of tert-butyl, or is Cs-C8cycloalkyl or methyl.

Compounds of the formula III in which G1 is methyl or cyclohexyl, in particular methyl, and G1 is tert-butyl or cyclohexyl, in particular tert-butyl, are preferred in particular.

2~900~2 Those compounds of the fo mula III in whieh n is a number from the range S to 8, for exnmple 6 to 8 and in particulllr the nutnber 6, are prefe~ed.

Further proeesses by which, or analogo~lsly to whicll, compounds of the fo rnula III and compounds of the t`o mul/l IV can be prepa~ed are described or .~ferred to in, for example, DE-~-2 147 544 and in NL-A-79-()5000.

As deseribed above, the radieal A in formula I is derived from a m-basie earboxylie aeid.
The aeids ean be aromatie, aliphatie, mixed aromatie-aliphatie, eyeloaliphatie or bieyeloaliphatie acids or unsaturated derivatives thereof, for example the following aeids:
eaprylic acid, aeetic acid, stearic aeid, polyisobutenyls~leeinie aeid, n-hexaeosanoie aeid, trimethylaeetie acid, propionic aeid, iso~ialeric acid, laurie acid, oleie aeid, aerylie aeid, methaerylie acid, sorbie aeid, linolellie acid, maleie acid, itaconie aeid, glutaeonie aeid, dibasie aeids~ sueh as oxalic aeid, sueeinie aeid, iso-dodeeylsueeinie aeid, glutarie aeid, adipie aeid, pimelie acid, suberic acid, azelic acid or sebacic aeid, tlle polymers of fatty aeids, sueh as the dimers and trimers thereof of the ~ype deseribed, for example, in Ind.
and Eng. Chem. 33, 86-89 (1941), hetero atom-eontaining aeids, for example, nitrilot;iaeetie aeid, eyeloaliphatie aeids, sueh as eyelohexaneearboxylie aeid, 1,2- and 1,~-eyelohexanediearboxylie aeid and naphthenie acids, ineluding, for example, eyelopentaneearboxylie aeid, eyelopentylaeetie aeid, 3-methyleyelopentylaeetie aeid, eamphor aeid, 4-methylcyclohexanecarboxylic aeid and 2,4,6-trimethylcyclohexanecarboxylic aeid, bieyelo[2.2.2]octa-5-ene-2,3-dicarboxylie aeid and bieyelo[2.2.1]hepta-5-ene-2-earboxylie aeid, aromatic earboxylie acids, sueh as ben~oie aeid, o-, m- and p-toluie aeid, phthalie aeid, terephthalic acid, trimellitie aeid, trimesie aeid, 1,2,4,5-benzenetetraearboxylie aeid, diphenie aeid, 1-naphthoie aeid~
2-naphthoie aeid, naphthalene-1,8-diearboxylie aeid, naphthalene-1,4-diearboxylie aeid, naphthalene-1,4,5-triearboxylie aeid and the like, paraffinie (d-aryl aeids, sueh as phenylaeetie aeid, hydroeinnamie aeid, phenylbuty~ie aeid, y-(1-naphthyl)butyrie aeid, ~-phenylene-n-valerie aeid, ~-phenyl-n-eaproie aeid, o-, m- or p-phenylenediaeetie aeid or o-phenyleneaeetie-~-propionie aeid, and also unsaturated phenyl aeids, for example, einnamie aeid.

Compounds of the formula Ia ~` 2~9~82 ¦ ~C~3)3C~R1 ~_ (C~2) ~ O--C A

in which n is lm integer from the range from 4 lo ~ and m is an inteuer from the range from 1 to 3, if m = 1, A is Cl-C2salkyl, which is unsubstiluted or substituted by Cs-C8cyclo~1kyl, or is C2-C2salkyl, whiçh is interrupted by Cs-C8cycloalkyl or one or more of the groups -S-, -O-and/or -NR2-, or, if m = 1, A is Cs-C8cycloalkyl, which is unsubstituted or substituted by Cl-CI2alkyl or C2-CI2allcenyl, C6-C8cyclonlkenyl, which is unsubstitu~ed or substituted by Cl-CI2alkyl or CrCI2aLkenyl, phenyl, which is unsubstituted or substituted by Cl Cl2alkyl or C2-CI2alkenyl, naphthyl, which is unsubstituted or substituted byCl-CI2alkyl or C2-CI2aLkenyl, biphenyl, which is unsubstituted or substituted byCl-CI2alkyl or C2-CI2a1kenyl, or A is C2-C2salkenyl, C6-C IObicycloalkenyl, C7-CI2phenylalkyl, C~CI2phenylalkcnyl, Cll-Cl6naphthylalkyl, Cll-Cl6naphthylalkenyl, Cl3-CI8biphenylalkyl, Cl3-CI8biphenylalkenyl, or a group of the lormula II

-CH2CHt~OH (Il), if m - 2, A is a direct bond, Cl-Cl2alkylene, C2-CI2alkenylene, C5-C8cycloalkylene, which is unsubstitutçd or substituted by Cl-CI2alkyl or C2-C~2alkenyl, or A ts C6-C8cycloalkenylene, which is unsubstituted or substituted by Cl-CI2alkyl or~
C2-C12alkenyl, or A is C6-ClObicycloalkenylene, phenylene, naphthylene or C2-CI8alkylene which.is interrupted by Cs-C8cycloalkylene or phenylene or at least one of the groups -S-7 -O- or-1~2-, if m = 3, A is Cl-C8alkanetriyl, C2-C8alkenetriyl, benzenetriyl, naphthalenetriyl, a trivalent group of the formula _ R~--N _ p~7 , or C2-CI8alkanetriyl which is interrupted by at least one of the groups -S-, -{)- or -NR2-, Rl is methyl or tert-butyl, ~90082 R2 is H or Cl-C4alkyl, R3 an(: R4, indcpendcntly of one another, are Cl-C4alkyl, and Rs, R6 and R7, independently o~ one another, are Cl-C3alkylene, are a prefcrred subjcct of the inVent;Otl.

Preferred compollnds of the formula I are those ill which n is an integel from the range frorn 4 to 8 and m is an integer from the range from 1 to 4; if m = 1, A is Cl-C25alkyl, which is unsubstituted or substituted by Cs-Cacycloalkyl; or C2-C2salkyl, which is interrupted by Cs^C8cycloaL~cyl or one or more of the groups -S-, -O- andlor -NR2-; or if m = 1, A is C5-C8cycloalkyl, which is unsubstituted or substituted by Cl-CI2alkyl;C6-C8cycloaLlcenyl, which is unsubstituted or substituted by C1-C~2alkyl; phenyl, which is unsubstituted or substituted by CI~CI2aLlcyl; or C2-C2 jalkenyl; C7-CI2phenylalkyl; or a group of the formula 11 - CH2 CH2~ OH (II), if m = 2, A is a direct bond; Cl-CI2alkylene; C2-CI2nlkenylene; Cs-C8cycloallcylene, which is unsubstituted or substituted by Cl-CI2alkyl; C6-C8cycloalkenylene, which is unsubstituted or substituted by Cl-CI2alkyl; phenylene; a divalent heterocyclic radical from the group comprising furan, thiophene or pyrrole, which is saturated on the nitrogen atom by hydrogen or the substituent R2; or, if m = 2~ A is C~-CI8alkylene which is interrupted by Cs-C8cycloalkylene or phenylene or at least one of the ;,roups -S-, -O- or -NR2-; and if m = 3, A is Cl-C8aLkanetriyl; C2-C8alkenetriyl; benzenetriyl; a trivalent group of the formula R5--N--R7_; or C2-CI8alkanetriyl, which ls interrupted by at least one of the groups -S-, -O- or-NR2-;
if m - 4, A is a benzene or cyclohexyl radical having 4 free valencies;
Rl and Rl, independently of one another, are Cl-ClOalkyl or Cs-C8cycloaLkyl;
R2 is H or Cl-C4aL~cyl;
R3 and R4, independently of one ano~her, are Cl-C4alkyl; and Rs, R6 and R7, independently of one another, are Cl-C3aLkylene.

2~082 Compounds of the formula I in whicll Rl is tert-butyl or cyclohexyl and Rl is methyl, tert-butyl or cyclohexyl;
n is n number from the range 4 to 6; ~md if m = 1, A is C6-Cl8alkyl or C2-Cl2alkenyl;
if m - 2, A is n clirect bond; Cl-CI2alkylene; phenylene; ~; or C2-C36alkylene inten~lpted by I to S oxygen or sulfur atoms;

if m = 3, A is benzenetriyl or a trivalent group of the formula _ CH - N C~ ; and if m = 4, A is a benzene radical having 4 free valencies, are a particularly preferred subject.

Amongst these compounds, compounds of outstanding importance are those in which, if m = 1, A is C2-CI2alkenyl; and if m = 2, A is phenylene; ~, C2-C36alkylene intermpted by 1 to 5 oxygen atoms; or a group -(CH2)k-S-(CH2)k-; and k is an integer from the range from 1 to 3; and in particular the compounds in which m is 1 or 2.

Compounds of the formula I which are also particularly preferred are those in which n is an integer from the range from S to 8, in particular from the range 6 to 8 and especially 6.

Amongst the compounds of the formula I, compounds of the formula HO OH
CH3 ~C(CH3)3 CHa ~C(CH3)3 ~CH2)6- O--C A C--O--(CH2)6 in which A is -(CH2)j-; -(CH2)k-S-(OEI2)k-; ~5~ or -(CH2)2-O-C(CH2)2-O-]j-~CH2)2- hat; j is O or an integer from the range from 1 to 4; and k is an integer from the range from 1 to 3, are particularly outstanding.

The following cornpounds in particular are of outstanding importance:

20~0082 a) 6-(3-tert-butyl-4-hydroxy-5-methylplletlyl)llexyl stearate;
b) fi-(3,5-di-tert-butyl-4-llydroxypllellyl)hexyl stearate;
c) bis[6-(3-tert-butyl-4-llydroxy-5-methylptlellyl)hexyl~ succillate;
d) bis[6-(3-tert-butyl-4-hydroxy-5-1llethylphenyl)hcxyll adipat¢;
e) bis[6-(3-tert-blltyl-4-hy(lroxy-5-metllylpllenyl)tlexyll suberate;
f) bis[6-(3-tert-butyl-4-hydroxy-5-metllylpllenyl)hexylJ isophthalate;
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] trimesate; and 1) tris[6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexyl] trimesate OH
(CH3)3C~ CH3 of the forrnulae I~J (a);
(CH2) 6 --C--C17H35 OH
(CH3)3C~C(C~13)3 I~J o (b);
(CH2) 6 --C--C~7H35 HO ~
CH3 _~C(CH3)3 CH3 ~,C(CH3)3 (CH2)6 0--C--(CH2)2--C-- -(CH2)6 HO OH
CH3 ~C(CHo)3 CH3 ~_C(CH3)3 (CH2~¢ 0--C--(cH2)4--C O -(ctl2)6 HO OH
CH3 _~C(CH3)3 CH3 ~ C(CH3)3 (CH2)6 0--C--(CH2)6--C--O -(CH2)6 2~9~0~2 OH OH
(CH3)3C~3,CH30 (CH3~3C~l,CH3 )6- 0--C--0--C--O (CH2)6 OH OH
(CH3)3C~c(cHa)3 (CH3)3C~,C(C~13)3 (CH2)6- 0--C ~ C--O (CH2~6 OH OH
(CH3)3C~,CH3 CH3 ~ C(CH3)3 (CH2)6-0--C,~ C--(CH2)6 \=< (h);
,C--0-~

CH3 J~C(CH3)3 OH

OH OH
(CH3)3C~3,C(CH3)3 (CH3)3C ~,C(CH3)3 (CH2)6- --C ~C-- '(CH2)6 \=~ (j); :
,C--O-~6 (CH3)3C J~C(CH3~3 OH

2~9~82 OH
OH CH3 ~J~ C(GH3)3 (CH3)3C~3,CH3 o ,~ C--O (CH2)6 (C~12)6- 0--C ~/ \~
\==< (k); nnd C--O -(CH2)6 O ~

CH3 ~C(CH3)3 OH
OH
OH (CH3)3C J~,C(CH3)3 (CH3)3C~[~, C(CH3)3 1.~

o J ~ c--o (CH2)6 (CH2)6- 0--C ~
\=( (1,).
C ~ O -(CH2)6 (GH3)3C ~C(CH3)3 OH

Compounds of the formula I in which n is an integer from the range 4 to 6; in particular those in which n is an integer from the range from 4 to 6 and in which, if m = 1, A is C6-C20alkyl, if m = 2, A is a direct bond, Cl-CIOalkylene, phenylene, or C2-C6alkylene interrupted by -S- and if m = 3, A is benzenetriyl are of particular Industrial importance.

A preferred subject of the invention also comprises cornpounds of the fo~mula I in which m is 2 and A is C4-C36alkylene Interrupted by at least one oxygen atom.

The compounds of the forrnula I in which, if m = 1, A is C6-C20alkyl, C3-CI8alkenyl, C6-C36alkyl interrupted by one or more -S- or -O- groups, cyclohexyl, cyclohexylsubstituted by Cl-C4alkyl, phenyl, phenyl substituted by Cl-Cl2alkyl, or phenylalkyl having a total of 7 to 9 carbon atoms, if m - 2, A is a direct bond, C1-CI2alkylene, C2-CI2alkenylene, phenylene, or C2-C36alkylene interrupted by a -S- or -O- group, and 20~82 if m = 3, A is Cl-C8alkanetriyl, benzenetriyl, alkylbcnzenetriyl of 7 to 10 carbon atoms, or C~2-CH2--N - Cl-l2 arc also importallt.

The compounds of thc formula I are suitable for stabilising organic materials against thermal, oxidative and actinic degradation, Reference is made in particular to their outstanding action as antioxidants in the stabilisation of organic materials.
Examples of such materials are:

1. polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- 1-ene, poly-4-methylpent- l-ene, polyisoprene or polybutadiene and also polymers of cycloolefins, for example, of cyclopentene or norbornene; and also polyethylene (which can be crosslinked, if desired), for example high density polyethylene (HDPE), low density polyethylene (Ll)PE), linear low density polyethylene (LLDPE) or branched low density polyethylene (BLDPE).

Polyolefins, i.e. polymers of monoolefins, such as are mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by diverse processes, in particular by the following methods:
a) free radical polymerisation (usually at high pressure and high temperature).

b) by means of a catalyst, the catalyst usually containing one or more metals ofgroups IVb, Vb, VIb or VIII. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which can be either ~- or ~-coordinated. These metal complexes can be free or fixed on a support, for example on activated magnesium chloride, titanium(II) chloride, aluminium oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerisation medium. The catalysts can be active as such in the polymerisation or further activators can be used, ~or example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of groups Ia, IIa and/or IIIa. The activators can, for example, be modified by further ester, ether, amine or silyl ether groups.

2 ~

These catalyst systems are llsually desi~nated Phillips, Standard Oil Indiana, Ziegler (-Nattn), TNZ (DuPont), metallncene or sin~le site catalysts (SSC).

2. Mixtllres of the polymers mcntione(l llnclcr 1), for ex~lmple mixtures of polypropylene with polyisoblltylcne, polypropylene with polyethylene (for ex~m1ple PP/~IDPE, PP/LDl'E~) nl)d mixt~lres of variolls types of polyethylene tfor example LDPF~ PE).

3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but~l-ene copolymers, propylene-isobutylene copolymers, ethylene-but-1-ene copolymers, ethylene~hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-b~tadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers,ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and also terpolymers o.f ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and also mixtures of such copolymers with one another and with polymers mentioned under 1), for example polypropylene/ethylene-prnpylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene acrylic acid copolymers, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolyrners and alternating or randomly composed polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifi~ations thereof (for example tacklfier resins) and mixtures of polyalkylenes and starch.

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

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and-alkyl methacrylate, styrene-maleic anhyclride and styrene-acrylonitrile-rnethyl acrylate; mixtures of high impact strength composed of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and also block copolymers of styrene, for 2~90~82 example styrene-blltacliene-styrene, styrene-isoprene-styrerle, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

7. ara~t copolymers of styrene or (x-methylstyrene, for example styrene on polybutadiene, styrene on polyblltadicne~styrene or polyb~ltadiene-acrylonitrile copolymers, styrene and ncrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonierile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and also their mixtures with the copolymers mentioned under 6), as are known, for example, as so-called ABS, MBS, ~SA or AES polymers.

8. ~alogen-containing polymers, for example polychloroprene, chlorinated rubber,chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homopolymers and copolymers, in particular polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride or polyvinylidene fluoride; and also tbeir copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

9. Polymers which are derived from a,~-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates impact-modi~led with butyl acrylate, polyacrylamide and polyacrylonitrile.

10. Copolymers of the monomers mentioned under 9~, with one another or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

11. Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl ben~oate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate and polyallyl rnelamine; and also their copolymers with olefins mentioned under point i.

2~90~82 ,() 12. Homopolymers and copolymers of cyclic ethers, sllch as polyalkylelle glycols, polyethylelle oxide, polypropylene oxide or thcir copolymers with bisglycidyl ethers.

13. Polyacetals, sncll as polyoxymethylelle"lnd also those polyoxymethylenes which contnin comonomers, for examplc ethylene oxide; polyacetals which are modified with thertnoplastic polyurethanes, acrylates or M~S.

14. Polyphenylene oxides and polyphenylene sulfides and their mixtures Wit}l 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, and their precursors.

16. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 619, 6/12, 4/6 and 12/12, polyamide 11, polyamide 12 and aromatic polyamides based on m-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and/or terephthalic acid and, if desired, an elastomer as modi~ler, for example poly-2,4,4-tlimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide.
Block copolymers of the abovementioned polyamides with polyolefins, olef1n copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. And also polyamides or copolyamides modified with EPDM or ABS; and also polyamides condensed during processing ("RIM polyamide systems").

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

18. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthala~e, and polyhydroxybenzoates, and also block polyether-esters which are derived frompolyethers having hydroxyl end groups; and also polyesters modified with polycarbonates or MBS.

209~2 - 2~) -19. Polycarbonates and polyester-carbonates.

2~). Polyslllfones, polyether-slllfones an(l polyether-ketones.

21. Crosslinked polymers wllich are derived from nldehydes on the one hand and phenols, ure~l or melamine on tlle other hand, sllch as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-forrnaldehyde resins.

22. Drying and non-clrying alkyd resins.

23. Unsaturated polyester resins which are denved from copolyesters of satllrated and unsaturated dicarboxylic acids with polyhydric alcohols and also vinyl compounds as crosslinking agents, and also their halogen containing modifications of low ~lammability.

24. Crosslinkable acrylic resins which are derived from sllbstituted acrylic acid esters, for example from 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. Crosslinked epoxy resins which are derived *om polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.

27. Naturally occurring polymers, such as cellulose, natural rubber, gelatin, and also the~r polymer-homologous chemically modified derivatives, such as cellulose acetates, cellulose propionates and celllllose butyrates, or cellulose ethers, such as methylcellulose;
and also colophony resins and derivatives.

28. Mixtures (polyblends) of the abovementioned polymers, for example PP/EPDM, polyamide/EPDM or AB~, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR, Pc!thermoplastic PUR, POM/a~rylate, POM/MBS, PPO/~IPS, PPO/PA 6.6 and copolymers, PA/~IDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic substances which are pure monomer 20go08~

compoun(ls or mixtures of such comyounds, for example mineral oils, animal or vegetable fats, oils and wa.Yes, or oils, waxcs nnd fnts bascd on synthetic esters (for exnmple phthalntes, ndipates, phospllntes or trimellitates), nnd nlso ndmixtures of synthetic esters with minernl oils in nrbitrnry proportions by wcight, such as are used, for example, as spinnillg prepnrntions, and also aqlleolls emulsions thereof.

30~ Aqueous emulsions of naturally occurring or synthetic rubbers, for example natural rubber latex or latexes of carboxylated styrene-butadiene copolymers~

Further subjects of the invention are, therefore, cornpositions containing an organic material sensitive to oxidative, thermal an(Vor actinic degradation and at least one compound of the forrnula 1, as well as the use of cornpounds of the ~ormula I for stabilising organic material against oxidative, thermal or actinic degradation~

The invendon therefore also comprises a method for stabilising organic material against therrnal, oxidative and/or actinic degradation, which method comprises adding at least one compound of the formula I to said material~

The use of compounds of the 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 such polymers, in particular thermoplastic polymers. Particularly preferred organic materials are polyolefins and styrene copolymers, for example those indicated above under points 1 to 3 and under points 5 and 6, in particular polyethylene and polypropylene and also ABS and styrene-butadiene copolymers. Composi~ions in which the organic material is a synthetic organic polymer or a mixture of such polymers, in particular a polyole~in or a styrenc copolymer, are therefore a preferred subject of the invention.

In general, the compounds of the ~ormula I are added to the material to be stabilised in amounts of from 0.01 to 10 %, preferably 0.01 to 5 % and in particular 0.01 to 2 %, with respect to the total weight of the material to be stabilised. The use of the compounds according to the invention in amounts of from 0.01 to 0.5 %, in particular 0.05 to 0.3 %, is particularly preferred.

209~082 In addition to the compoun~ls of tlle ~ormul~l 1, the compositions according to the invention can additionally ColltLlill conventional additives, for example those indicated below.

1~ Antioxi(lants I.1. a!kylntecl-!n~ for example 2,6-di-tert-blltyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-blltyl-4-etllylpllenol, 2,6-di tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(a-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-t~i-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(l'-methyl-undec-l'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-heptadec-1'-yl)phenol, 2,4-di-methyl-6-(1'-methyl-tridec-1'-yl)phenol and mixtures the;eof~

1.2, Alkylthiomethylphenols, for example 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-do-decylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkvlated hYdroquinones, for example 2,6-di-tert-butyl-4-rilethoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-'n~ydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hy~roxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. HydroxYlated thiodiphenvl 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) disulffde.

1.5. AlkYlidene-bis~,ahenols, 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-methyl-cyclohexyl)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-di-methylbenzyl)-4-nonylphenol], 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-~0082 methylene-bis(6-tert-butyl-2-methylphcnol), 1,1-bis(S-tert-butyl-4-hydroxy-2-methyl-phellyl)butane, 2,6-bis(3-tert-blltyl-S-methyl-2-hydroxybenzyl)-4-metllylphenol, 1,1,3-tris(S-~ert-blltyl-4-llydroxy-2-metllylptlellyl)blltane~ 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphellyl)-3-n-clodecylmercaptobutlllle, ethylene ~Iycol bisL3,3-bis(3'-tert-butyl-4'-hydroxypllenyl)blltyr.lte], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-57-llletllylbenzyl)-6-tert-butyl-4-methylphenyll tere-phthalate, t,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propflne, 2,2-bis(S-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutane and l,1,5,5-tetra(S-tert-butyl-4-hydroxy-2-methylphenyl)pentane .
1.6. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, and isooctyl 3 ,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.7. HYdroxvbenzYlated malonates, for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, di[4-(1,1,3,3-tetramethylbutyl)phenyl~ 2,2-bis(3,S-di-tert-butyl-4-hydroxybenzyl)malonate.

1.8. HYdroxybenzyl-aromatic compounds? for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol .

1.9. Triazine compounds, for example 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1 ,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) 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 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

2 ~ 2 ,~,~lospholultes~ for example dim~thyl 2,~-di-~ert-blltyl-4-hydro~ybenzylpllosphollate, diethyl 3,5-di-tert-butyl-4-hydroxybellzylpl-osphonatc, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylpllosphollate, dioctadecyl S-tert-blltyl-4-hydroxy-3-methylbenzylphos-phollate and the calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxyben~ylphosphonate.

1.11. AcYlaminophenols, for example 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.12 Esters of ,B-(3~5-di-tert-butyl-4-hYdroxvphenYl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaelythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiallndecanol, 3-thiapentadecanol, tri-methylhexanediol, trimethylolpropane and 4-hydroxymethyl- 1-phospha-2,6,7-tri-oxabicyclo[2.2.2]octane.

1.13. Esters of ~-~S-tert-butYI-4-hYdroxY-3-methvlPhenyl)propionic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, tri-methylhexanediol, trimethylolpropane and 4-hydroxymethyl- 1 -phospha-2,6,7-tri-oxabicyclo[2.2.2]octane.

1.14. Esters of ~-(3~5-dicYclohexvl-4-hYdroxyphenYl)propionic ac d with monohydric or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, tri-methylhexanediol, trimethylolpropane and 4-hydroxyrne~hyl-1-phospha-2,6,7-tri-oxabicyclo[2.2.2]octane.

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, octadecanol, 1,6-hexanediol, 209~082 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopcntyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)etllyl isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaunclecallol, 3-thiapentadecanol, tri-methylllex~ ediol, trirnethylolpropane and 4-hydroxymetllyl- 1-phospha-2,6,7-t~i-oxabicyclo~2.2.2:1octane.

1.16. Amides of ~ (3~$-di-tert-butvl-4-hvdroxyphenvl)propionic acid, for example N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-b~ltyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N'-bis(3,5-di-tert-b~ltyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV-absorbers and li~ht stabilisers 2.1. 2-(2'-HydroxYPhenvl)benzotriazoles, for example 2-(2'-hydroxy-5 '-methylphenyl)benzotriazole, 2-(3 ' ,5 '-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5' tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5 '-(1,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 ' ,5 ' -di-tert-butyl-2 ' -hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5 '-methylphenyl)-5-chlorobenzotriazole, 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,o~-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2' -hydroxyphenyl)-5-chlorobenzo-triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2' -hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-(3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesteri~lcation product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-2~9~0~2 hydroxypllenyllbenzotriazole with polyethylellc ~Iycol 300; [~-CH2CH2-COO(C~12)3~, whcrc R=3'-tert-bu~yl-4'-hydroxy-5'-21-1-bcllzotrinzol-2-ylphenyl.

hellolle, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyl-oxy, 4-do(lecyloxy, ~l-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy delivative.

2.3. Esters of substituted or unsubstitute_benzoic acids, for example 4-ter~butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis~4-tert-butyl-benzoyl)resorcinol, benzoylresorcinol, 3,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben~oate and 2-me~hyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl and isooctyl ~-cyano-~"~-diphenylacrylate, methyl oc-carbomethoxycinnamate, methyl and butyl a-cyano-,B-methyl-p-methoxycinnamate,methyl cc-carbomethoxy-p-methoxycinnamate and N-~,B-carbomethoxy-~-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphGnic ~cid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxime and nickel cGmplexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if desired with additional ligands.

2.6. Sterically hindered amines, for example bis(2,2,6,6-~etramethylpiperidyl) sebacate, bis(2,2,6,6-tetramethylpiperidyl) succinate, bis(1,2,2,6,6-pentame~hylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetra-methyl-4-piperidyl) 1,2,3,4-butanetetraoate, I, I '-( I ,2-ethanediyl)bis(3,3,5,5-tetr.ullcthylpipcr~zinone), 4-bcn;~oyl-2,2,6,6-tetratnetllylpiperidinc, 4-stc~ryloxy-2,2,6,6-tetramethylpiperidine, bis(l,2,2,6,6-pent.lmethylpiperidyl) 2-n-blltyl-2-(2-llydroxy-3,5-cli-tert-butyl-benzyl)malonnte, 3-n-octyl-7,7,9,9-tetrnmethyl-1,3,8-trinzaspiro[4.51decane-2,4-dione, bis(l-octyloxy-2,2,6,6-tetrametllylpiperidyl) sebncnte, bis(l-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, the condensation product of N,N'-bis~2,2,6,6-tetramethyl-4- piperidyl)llexametllylenediamine and 4-morpholino-2,6-dichloro- l ,3,5-triazine, the condensation product of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensation product of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[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-penta-methyl-4-piperidyl)pyrrolidine-2,5 -dione .

2.7. Oxalic acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-S,S'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and also of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-~ydroxvphenYI)-1.3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl~- 1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl~-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3 ,S -triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyl-oxy)phenyl]-4,6-bis(2,~-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl~-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, 2al90082 N,N'-diacetyladipic acid dillydrazide, N,N'-bis-salicyloyloxalic acid dihydrazide, and N,N'-bis-salicyloylthioyropionic acid dihydrazi(le.

4. F~urthe ~sphites ~Ind phosl)honites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris~nonylphenyl) phosphite, trilautyl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, ~ris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(~,6-di-tert-butyl-4-methylphenyl)pentaerythlitol diphosphite, bis-isodecyloxypenta-erythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12~-dibenz[d,g]-1,3,2-dioxaphospnocin and 6-fluoro-2,4,8,10-tetra-tert-butyl- 12-methyldibenz[d,g~- 1 ,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylyhenyl) methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

5. Peroxide-destrovin~ compounds, for example esters of ,t3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis(,B-dodecylmercapto)propionate.

6. PolYamide stabilisers, for example cupper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic costabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate,sodium ricinoleate, potassium palmitate, antimony pyrocatechinate or tin pyrocatechinate.

8. Nucleatin~ ag~nts, for example 4-tert-butylbenzoic acid, adipic acid and diphenyl acetic acld.

9. Fillers and reinforcin~ algents, ~or example ~alcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black and graphite.

- 2'~ -__~ciitivcs, for example plasticisers, lubrica-lts, emulsifiers, pigments, fluorescent wilitenillg a~ents, flallleproofillg ngellts, nntistatic agents all(l propellants.

11. 1~5~n(iol _lles, as clescribed, tor exnmple, hl US-A-4 325 863 or US ~-4 338 244.

The conventional additives are added, for example, in concentrations of from 0.01 to 10 %, with respect to the total weight of the material to be stabilised.

The incorporation of the compound of the formula I and, if desired, further additives in the organic material is effected by known methods. Incorporation into the materials can, for example, be effected by mixing in or applying the compounds of the formula I and, if desired, further additives using the methods customary in the art. 1~ the materials are polymers, in particular synthetic polymers, the incorporation can be effected before or during shaping, or by applying the dissolved or dispersed compounds to the polymer, with subsequent evaporation of the solvent where appropriate. In the case of elastomers, these can also be stabilised AS latexes. A further possibility for incorporatin~ the compounds of the formula I in polymers comprises adding said compounds before, during or immediately following the polymerisation of the corresponding monomers or prior to crosslinking. The compounds of the formula I can be added as such, but also in encapsulated form (for example in waxes, oils or polymers). In the case of addition before or during the polymerisation, the compounds of the formula I can also act as regulators for the chain length of the polymers (chain stoppers).

The compounds of the formula I can also be added to tho materials to be stabilised in the forrn of a masterbatch which contains said compounds, for example in a concentration of from 2.5 to 25 % by weight.

The materials stabilised in this way can be used in very diverse forms, for example in the form of films, fibres, tapes, m'dulding compositions or sections or as binders for coating compositions, adhesives or putties.

The following examples further illustrate the invelttion. Unless indicated otherwise, parts and percentage data in these examples are by weight. In the formulae the prefix n designates a straigllt-chain alkyl radical and the prefix i a mixture of isomers. "Melting 209~082 point" is abbreviated ns "m.p." in thc tables.

Ex~: Prepara~ion of 4-~3-ter~-hutyl-5-methyl-4-llydroxyphellyl)butimol.SO g of potassillm hy(lro~ide, 316 g of 2-tert-butyl-6-Metllylphenol and 866 g of 1,4-butnnediol are initially inLroduced into an autoclave. Af~er introdllcing nitrogen gas, the mltoclave is close(l nnd the mixture is heated at 235C t4 bar) for 6 hours, with stirring; n further rise in prcssure as a consequence of the reac~ion is prevented by blowing of gas. When the reaction is complete, the reaction mix~ure is cooled to 80C and the autoclave is emptied. Excess butanediol is rcmoved by distillation. The distillation residue is poured into 1 1 of water and S00 ml of toluene. The organic phase is then washed with water until neutral and the toluene is stripped ot`f by applying a vacuum. The remaining residue (310 g) contains 68-70 % of the title product of the formula OH
(CH3)3C~,CH3 CH2 CH2~ ~OH

Further purification is effected by f~actional distillation under vacuum: the pure product boils at 115C and 35 Pa (= 0.35 mbar). It has a refractive index n20D of 1.5322.

Example lb: Preparation of 6-(3-tert-butyl-5-methyl-4-hydroxyphenyl)hexanol.
Example la is repeated except that in place of 1 j4-butanediol an equivalent amount of 1,6-hexanediol is used. The resulting product of the formula OH
(CH3)3C~CH3 has a boiling point at 35 Pa (= 0.35 mbar) of 135C and (CH2)6--OH
melts at 45C.

Example lc: A solution of 25.5 g (84 mmol) of stearoyl chloride in 10 ml of toluene is added dropwise at 10C, under nitrogen, to a solutlon of 18.9 g (80 mmol) of 4-(3-tert-butyl-5-methyl-4-hydroxyphenyl)butanol (product from Example la) and 9.5 g 2~90~82 (120 mmol) of pyridine in 90 ml of toluene. The white suspension is then allowed to warm to 20-25C mld filtered and thc filtrate is poured into approximately 1 mok~r aqueous HCI
and extracted wi~l ethyl acetate. Af~er drying an(l concentrating the organic phase, the resulting crude product is purit`ied by chromntography (siO2; hexane:ethyl acetate = 19:1).
0~1 (CH3~3C ~,CH3 37.2 g (93 %) of the product of the formula (C~12)4 0--C - n cl7l~35 (compound No. 1) are obtained in the form of a colourless liquid. Characterisation (IR) and analysis are given in Table 1.

Examples 2-16: In order to prepare compounds Nos. 2 to t6, corresponding t~-(3-tert-butyl-5-methyl-4-hydroxyphenyl)alkanols or co-(3,5-di-tert-butyl-4-hydroxyphenyl)alkanols are first synthesised by the method described in Example la. The starting compounds (compounds of the formula IV) thus obtained are then reacted using corresponding acid chlorides in accordance with the methotl descri~ed in Exarnple lc to give the said end praducts (compounds of the formula I). Data on the purity and characterisation of the compounds are summarised in Tables 1 and 2. Where no melting point is indicated, the compounds are liqùid at room temperature.

Tclb. 1: Analytical and IR data Ior compounds Nos. 1-8 OH
(CH3)3C~,~,CH3 CompoIlnd t.ype: ~
(CH2)~r 0--C ~--A

__ _----~ ANALYSIS: IR~
Compouud. n A ~O C: calc. foul~d % H: C~lc. found C=O [cm 13 _~
1 4 -n-Cl7~3s 78.8 78.7 11.6 l l .4 1738 2 4 -n-c7H1s 76.2 76.1 10.6 I0.~ 1719 3 4 -i-c7H1s 76.2 76.2 10.6 11.0 1717 4 4 -i-Gl2~C22H 77.7 77.7 11.2 11.1 1717 4 - CH2 CH- CH~ C2Hs 76.2 76.0 10.6 10.4 1715 6 6 - CH2 - CH- cH2 - C2Hs 76.9 76.9 10.8 10.6 1715 7 6 -n-C11H23 78.0 77.9 11.3 11.5 1732 8 6 -n-Cl7H3s _ 79.2 79.1 11.8 12.2 1720 2 ~ 2 Tab. 2: Melting points, analytical ancl IR data ~o~ compollnds Nos. 9- l 6 OH
(CH3)3C~,~ C(C~3)3 Compoun(ltype: ~
~CH2)rr 0 ~ A

_ _ ~NALYSIS: IR: 1/ A
CmNPound n C2Hs m.p ['CI % C: c~c. found % H: cnlc. found C=0 ¦om'~¦

9 4 - CH~ CH- CH~ C2Hs 77.2 77.0 11.0 10.8 1732 4 -1)~G7H1 ~ - 77.2 77.2 11.0 11.4 1736 11 4 -i'C12H25 . 78.4 78.3 11.5 11.5 1735 12 4 'n C17HSS 30-33 79,4 79,5 11.8 12.1 1738 13 5 ~n'C17HH5 31-32 79.5 79.6 11.9 11.9 1738 14 6 - cH~cH-cH~c2H6 77,7 77.7 11.2 1 I.5 1738 6 -n-C11H23 7~,6 78.5 11.6 11.9 1737 16 6 -n-C17H35 35 79,7 79.6 12.0 12.2 1738 Exarnple 17: 13.6 g (0.074 mol) of adipic acid dichloride are added dropwise at 10C
under nitrogen to a colourless solution of 33 g (0.14 mol) of the product from Exarnple la and 16.6 g (0.21 mol) of pyridine in 200 ml of toluene in a 350 ml sulfonation flask. The mixture is then allowed to warm to room temperature9 while continuing to stir. After 2 h the reaction mixture is poured into aqueous hydrochloric acid and extracted with ethyl acetate. After drying and concentrating the organic phase, the resulting crude product is purified by chromatography (siO2; hexane:ethyl acetate = 19:1). 36 g (88 %) of the product (compound No. 17) of the formula - 2090~82 OH OH
(CH3)3C~,c~l3 C~3 ~ C(CH3~3 ~l o o l~J . whicll has a meîting point tCH2)4--o--c--(CH2)4--C O -(CH2)4 of 50-52C are obtained Charnc~elisation (IR) an(l analysis are given in Table 3.

_xamples 18-22 and 24-34: In order to prepare compounds Nvs. 18 to 22 and 24 to 34 corresponding ~-(3-tert-butyl-5-methyl-4-hydroxyphenyl)alkanols or ~o-(3 5-di-tert-butyl-4-hydroxyphenyl)alkanols are first synthesised by the method described in Example la. The starting compounds (compounds of the formula IV) thus obtained are then reacted using conesponding dicarboxylic acid dichlorides in accordance with the method described in Example lc to give the said end products (compounds of the formula I). Data on the purity and characterisation of the resulting compounds are summarised in Tables 3 4 and 5.

Example 23: 4.98 g (30 mmol) of isophthalic acid 14.4 g (70 mmol - 2.3 equivalents) of dicyclohexylcarbodiimide and 150 ml of dichloromethane are mixed at 20-25C under nitrogen in a 750 ml sulfonation flask. A solution of 15.9 g (60 mmol = 2 equivalents) of 6-(3-tert-butyl-5-methyl-4-hydroxyphenyl)hexanol (product from Example lb) in 80 ml of dichloromethane and a solution of 0.73 g (6 mmol) of dimethylaminopyridine in S ml of dichloromethane are added to the resulting white suspension. The mixture is refluxed for 4 hours. It is then cooled to 20-2~C and filtered and the filtrate is evaporated. The resulting crude product (viscous oil) is purified by chromatography (SiO2; hexane/ethyl acetate =
1~/1). 11.3 g (57 %) of compound No. 23 are obtained in the form of a colourless oil. Data on the purity and characterisation are given in Table 3.

209~2 Tab. 3: Melting points, analytical and IR dati1 for compollnds Nos. 17-23 OH OH
(C~13)3c~cH3 C~3 ~C(CH3)3 Compoun(l ~ypc: 1~1 ~1 (CH2)1~ 0 - C--A ~ C ~ O -(CH2)n . _ _ ANALYSIS: îR: 1/ A
Com~ound n . ID p.¦ Cl % C: cslc. fouod % H: calc. found C=O ¦cm'~

17 4-(CH2)4- 50-52 74.2 73.8 09.3 09.5 1718 18 4-(CH2)g- ~ 75.2 74.7 09.8 09.9 1717 19 6 . 74.2 74.1 09.3 09.7 1738 6-(CH2)2' 90-103 74.7 73.9 09.6 09.8 1713 21 6-(CH2)4- 91 -95 75.2 75.0 09.8 09.7 1718 22 6-(CH2)g- 76.0 75.5 10.2 10.2 1718 23 6 ~ - 76.6 76.1 08.9 09.1 1723 2~9~82 - ~6 -Tab. 4: Meltin~ pC)illtS, analyliclal allcl IR (I,ata tor compounds NC)S. 24-3() 0~1 01-1 (CH3)3C~ C(CH3)3 (CH3)3c~,c(cH3)3 Compouncl lype:
(CH2)jr 0--C--A--C--O -(CH2)n _~ ANALYSIS: IR~
No. n A m.p.[~c] % C: calc. found % H: calc. found C=O [cm'1]
. _ _ 24 4 -(CH2)4- 86-88 75.6 75.5 10.0 09.8 1734 89-90 75.2 75.1 09.8 os.s 1743 26 5 -(CH2)4- 92-95 76.0 75.6 10.2 10.0 1735 27 6 76.6 75.7 10.0 10.1 1743 28 6 -(CH2)2- 70 76.0 75.9 10.2 10.4 1736 29 6 -~CH2)4- 54~57 76.4 76.5 10.3 10.6 1735 6 -~CH~ 77.1 77.1 10.6 10.6 1735 2 0 ~ 2 Tab. 5: Analy~ical and IR data for compounds Nos. 31 to 34 Compound type:
OH OH
(C1~3)3C~,R1 R~ c(CH3)3 (CH2),r 0--C--(CH2)r S--(CH2)r C--O ~(CH2)n _ _ AN~LYSIS:IR. 1/ A
No. n R1 i yO C: c~lc. found % H: c~lc. found % S: c~lc. found C=O [cm 1]
31 4 CH3 2 70.3 70.5 8.9 9.05.2 5.4 1731 32 6 CH3 2 71.6 71.5 9.3 9.54.~ 4.9 1732 33 6 C(CH3)3 2 72.7 72.6 9.7 9.7 4.4 4.7 1736 C(CH3)3 1 72.1 72.0 9.5 9.6 4.6 4.7 1734 Example 35: Example 23 is ,repeated except that in place of the product from Example lb 6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexanol is used as the starting material. The product (compound No. 35) of the formula OH OH
(CH3)3C~ C(CHg)3 (CH3)3C~¢~C(CH3)3 (C~2)6--O--C ~ C--O -(CH2)6 has an IR absorption of the carbonyl band at 1723 cm~l.
Analysis: calculated 77.6 % C 9.5 % H, found 77.1 % C 9.5 % H.

xample 36: 7.57 g (30 mmol) of methyl trimellitate, 33 g (117 mmol) of the product from Example lb and 0.45 g (1.8 mmol) of dibutyltin oxide are mixed in a round-bottomed ~90082 flask fitted with a fracliollating column. Thc mixture is heale(l ~o I X0C, metlmnol being distilled off. After 2 hours the pressure abovc ll-c rnixlllrc is r~dllce(l to 533 hPa (= 400 mmHg) and the temper~lllrc is then kcp~ ~It 180C t`or a t`~lrlhcr ~ hollrs. The excess 6-(3-tert-butyl-S-methyl-~-hydroxyphenyl)llexnnol is lhell removed by dislillation (150C, 4 Pa) antl the resulting cru(le product is purit`ied by chromatograplly (SiO2; first hexane, ttlell hexnne/ethyl ncetate = 19/1). 24.7 g (87 %) ot` a prodllct of the formula OH OH
(CH3)3C~3,CH3 CH3 ~,C(CH3)3 (C~l2)6- 0--C ~ C--O (C~I2)6 C--O -(Cl2)6 CH3 J~C(CH3)3 01~

(compound No. 36) are obtained; IR absorption of the carbonyl band at 1722 cm-l.Analysis: calculated 75.9 % C 8.9 % H, found 75.3 % C 9.3 % H.

xarnple 37: 16.5 g (70 mmol) of 4-~3-tert-butyl-S-methyl-4-hydroxyphenyl)butanol, 18.05 g (91 mmol) of methyl 10-undecenoate and 80 mg (1.4 mmol) of dibutyltin oxide are introduced into a round-bottomed flask fitted with a fractionating column.

The mixture is heated to 180C, methanol being distilled off. After 2 hours, the pressure above the mixture is reduced to 400 mmHg and the temperature is then kept at 1 80C for a further 2 hours. The excess methyl 10-undecenoate is then removed by distillatiorl and the resulting crude product (brown oil) is purified by chromatography (SiO2; hexane/ethyl acetate 9:1).

23.15 g (82 %) of a product of the formula ~90082 H3C ~ C ~ 3 OH
Ch3 ~C~3 (C~2)4 o ", (CH~)b C~
ll CH2 are obtained.
Anfllytical and IR data: see Table 6.

Examples 38-42: Compounds 38-42 are prepared analogously to lhe method described in Example 1. Analytical and IR data of cornpounds 38-40 are given in Table 6 and the corresponding data for compounds 40 and 41 are given in Table 7.

Tab. 6: Analytical and IR data for cormpounds Nos. 37-40; cornpound type:

OH
(CH3)3C~ CH3 O
(CH2)~--0--C--A
_ __ _ . _ -: _ ANALYSIS: IR~
No n A % C: c~c. found % H: c~c. found C=O [cm _ __ ~ _ _ _ 37 4 -(CH2)8-CH=CH2 77.56 77.59 10.52 10.58 1719i1735 38 4 -C(CH3)~CH2 74.96 74.95 9.27 9.48 1705 39 6 -CH=CH2 75.43 75.20 9.50 9.53 1712l1725 .
6 -C(CH3)=CH2 75.86 75.83 9.70 10.16 1705/1718 ~0082 - ~o -Tab. 7: Ana1y~ical and IR ~ata for compollnds Nos. 41 and 42 OH
(CH~)3C~,~C(c~13)3 Compoulld ~yp~
(CH2)~r 0--C A

_ _ . _ _ ANALYSIS: IR: 1/ A
No. n . _ _ % C: calc. fo~ d % H: calc. found C=O ¦Gm ~¦
41 6 -C~H=CH2 76.61 76.44 10.06 10.08 1725 42 6 -C(CH~)=CH2 76.96 76.85 10.23 10.16 1719 Exam~es 43-4S: Compound No. 43 is prepared by the method described in Example l;compound No. 44 is prepared by the method described in Example 37; compound No. 45 is prepared by the method described in Example 23. Analytical and IR data for compounds 43-45 are given in Table 8.

Tab. 8: Analysis and IR data for compounds Nos. 43-~5 OH OH
(CH3)3C ~,CH3 CH3 ~C(CH3)3 Compound type: l~ 0 l~) (CH2~n C--A--C--~(CH2)n .
_ ANALYSIS: IR~
No. n A % C: calc. found % H: calc. found C=O ¦cm~1]
_ _ _ ~
43 4 -CH2-CH2- 73.61 73.14 9.08 9.21 1722 44 4 -(CH2)2-O-(CH2)2- 72.21 71.93 9 09 9.20 1728 6 ~ 72 .25 72.41 8.49 8.53 1717 _ _ _ %S: calc.4.82 found 4.69 _ 2090~82 Example 46: ~? Esterit`ic~tion ol` the dicarboxylic acid mixtule with methanol 22 ml/0.4 l mol of concentl llted sulfuric acid are added dropwise at 10C~ to a solution of 52 g ~0.4 mol) ot` dicarboxylic aci(l mixtu~e (mnmlfacturer B~SF; comprising 25-35 % of SUCCitliC acid, 37-47 '~, of glutaric ncid and 25-30 % ot' adipic acid) in 450 ml of methanol.
Thc reslllting solution is kept at the reflux temperatl1re for 3 hours. After cooling to 20-25C, the mix~llre is neutralised Wittl SS g of potassium carbonate, poured into water and extracted with ethyl acetate. Evapor~tion of the solvent yields 23 g (36 %) of the desired ester mixture in the form of a pale yellow oil.

Gas chromatographic analysis of the compound mixture of the formula H3C-OCO-(CH2)~-COO-CH3:

x = 2 23 mol-%
x-3 44mol-%
x = 4 33 mol-%

b) Preparation of compound 46 30.7 g (130 mmol) of 4-(3-tert-butyl-5-methyl-4-hydroxyphenyl)butanol, 8.01 g (50 mmol) of the diester mixture described under (a) and 490 mg (2 mmol) of dibutyltin oxide are introduced into a round-bottomed flask provided with a fractionating column.
The mixture is heated to 180C, methanol being dis~lled off. The mixture is kept at 180C
for a further 15 hours. After cooling to 20-25C, 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.
Analytical and IR data: see Table 9.

Examples 47-Sl: The preparation of compounds 47-48 is carried owt using corresponding phenolic alcohols in accordance with the method described in Example 46.

In order to prepare compounds 49, 50 and 51, the corresponding methyl ester is first synthesised from Poly-THF-Dipropionic acid~ 350 (manufacturer: Bayer A.G., Leverkusen) by the method described in F,xample 46. The high molecular weight ~090~82 dicarboxylic aci~l methyl estel thus obtained is then re~ctecl using currespon~ting phenolic alcohols in accordanc~ wilh the method c!escribed in Example 46 to give the said end pro(lucts.
Annlytical and IR datn for compollnds 46-51 ar~ given in Tnble 9, Table 9: Analytical ~m~l IR (lata tor compoun(ls 46-51 Compound type (diester mixtures and oligomers) ~CI ~2) n (Cl H2) n O ll A 11 - O
O O
_ _ ~ _ _ Com- ANALYSIS: IR~
~und R 1 n A C %: H %: C-O [cm 1]
No. _ _ calc. foundcalc. found 46 Me 4 ~ where X = 2 20-25% 73.91~ 73.79 9.22 9.37 1719 47 t-Bu 4 J - (CH2)X x - 3 40 43% 75.43~ 75.05 9.88~ 9.98 1735 48 Me 6 21 % x=2; 42% x=3; 37% x=4; 74.96~ 74.91 9.68b 9.81 1720 m.p.79-93 C
49 Me 4 70.26 69.92 9.61 9.78 1735 t-Bu 4 - (CH2~2 O ~ (CH2)4- O ~y (CH2)2 - 71.87 71.92 9.95 10.21 1737 51 Me 6 y - 2.6 71.70 71.18 9.96 9.97 1736 Me = methyl; t-Bu ~ tert-butyl ~ Analysis calculated for x = 3 ~9~82 le 52: u) Prcpar.~ ?n Or me~hYl n_rilolriaccl~

7~.8 n~l (137.7 ~; 1.4 ~lol) of collcen~ra~e(l sulrllric aci(l nre a(lde(l dropwise to a sllspensioIl of l()0 ~ (0.52 mol) of nitrilolrincelic aci(l in ')00 ml of methnllol nt about lOC.

The mixturc is kept at the reflux temperature for 22 hours. After cooling to room temperature, the mixture is neuLralised by careful addition of 150 g of potassium carbonate, poured in~o water and extracted with ethyl acetate.

Evaporation of the solvent and drying of the residue under vacuum yields 57 g (47 %) of methyl nitrilotriacetate in the form of a colourless oil.

IR (film on KBr crystal): carbonyl absorption at 1751 cm-Analysis: calc. 46.35 % C, 6.4~ % H, 6.0 ~O N
found 4~S.47 % C, 6.53 % H, G. 14 % N

b) Preparation of compouncl 52 1.76 g (7.5 mmol~ of methyl nitxilotriacetate, 7 g (29.4 mmol) of 4-(3-tert-butyl-5-methyl-4-hydroxyphenyl)butanol and 25 mg (0.45 mmol) of dibutyltin oxide are introduced ~nto a round-bottorned flask provided with a fractionating column.
The mixture is heated to 180C, methanol being distilled of After 3 hours, the pressure is reduced to 400 mmHg and the mixture is kept at 180C for a further 2 hours.

The excess 4-(3-tert-butyl-5-methyl-4-hyd~oxyphenyl)butanol is then removed by distillation (150C/0.4 Pa) and the resuldng crude product is purified by chromatography (siO2; hexane-ethyl acetate 9:1_3:1).

5.6 g (88 %) of a product of the formula ~9~

- 4~ -c~C~13 (CH2)4 o~CH2----N

are obtained.
Analytical and IR data: see Table 10.

Examples 53-SS: Compounds 53-55 are prepared by the method desclibed in Example 52.
Analytical and IR data of the compounds are summar~sed in Table 10.

'CCH~ R 1 Table 10: Compound ~ype (C, H2)n O~rCH2~--N

Com- _ -- ~ ANALYSIS: IR~
pound Rl n m.p. C%: H%: N%: ~ C_O [cm-1]
No. calc. found calc. found calc. found 52 Me 472.39 72.39 8.93 8.83 1.66 1.48 1738 53 t-Bu 474.11 73.42 9.64 9.68 1.44 1.23 1747 54 Me 673.59 72.98 9.43 g.67 1.51 1.31 1739 t-Bu 675.03 74.18 10.02 10.28 1.33 1.33 1748 _ . _ ~ ~

Examples 56-60: Compounds 56-60 are prepared by the method described in Exarnple 36.
Analytical and IR data of the eompounds are summssed in Table l l.

2~90~82 T~lble~ Compo~ l ty~ R~
(C~l2)6 ~--A

_ _ ~ _ ~ ANALYSIS: IR 1/ A
pOoum~d R1 A z tn.p.-Cc%: H%: C=O [cm-~]
No. _ _ c~lo. found c~lc found 56 t-Bu ~ 3 77~05 77.28 9.56 9.53 1727 57 Me ~ 3 62-6575.91 75.95 8.92 8.92 1728 58 ~ I ~ 1 ~95 91 77.~6 76.09 9.5 9.67 1 7~9 59 Me ~ 4 75.57 74.95 8.94 9.65 1725 60 t Bu 4 ~ 76.77 71.14 9.69 6.91 1730 Example 61: Preparation of 4-(3.5-dicyclohexYl-4-hYdroxyphenYl)hexanol 258 g (1 mol) of 2,6-di.cyclohexylphenol and 591 g (5 mol) of 1,6-hexanediol are melted in a sulfonation flask and heated with 36 g (0.64 mol) of potassium hydroxide for 10 hours at 238C. The mixture is then slightly acidified at 80C using a 2 molar aqueous HCl solution. The phases are separated, the inorganic phase is washed with toluene and the combined organic phases are concentrated in a rotary evaporator. Excess 1,6-hexanediol and unreacted 2,6-dicyclohexylphenol are removed by distillation.

2nsoos2 Crystallisation of the resi(llle from special boiling point ben~.ine (80- l l0C) yields 163 g (45 %) of a prodllct of the formukl (f H2,6 OH

m.p.: 96C
Analysis: calc. 80.39 % C, 10.68 % H
found78.62%C, 10.62%H

Example 62: 32.3 g (90 mmol) of 4-(3,5-dicyclohexyl-4-hydroxyphenyl)hexanol are reacted using 9.2 g (50 mmol) of adipic acid dichloride, in accordance with the method described in Example lc, to give 18.7 g (47 %) of a product of the formula C,~,C C~

(CH2)6 (ci~2)6 l I :
O C (CH2)4 11 -O O

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

IR (film on KBr crystal~: 1736, 1717 cm-l (C = Oj Analysis: calc.77.76 % C, 10.29 % H
found 77.62 % C, 10.05 % H

20~0082 Vse ,examples ,Exam~,: _a_s tl of polypropYlenc 100 parts of polypropylelle powder, con~ailling 0.1 % ot`calcium slearate, are mixed with 0.3 % of distearyl thiotlipropion.lte ~DS rDp) ~u~(l o~ l % of the stabiliser according to the invention indicate(l in Tablc 12 antl the mixlure is ~hen kneaded for 1() minllteg at 200C
in a Brabender pklstogr.lph.

The composition thus obtained is pressed in a press which has a surf.lce temperature of 260C to give l mm thick plates, from which strips l cm wide and 10 crn long arepunched. For comparison purposes, a further sample is prepared without stabilisers.
Several such strips from each plate are suspended in a circulating air oven heated to 135C
or 149C and observed at regular intervals. The oxidative decomposition of these strips can be recognised by an incipient circular yellow discoloration. The time in days until decomposition takes place is a criterion for the stability of the sample.

Table 12: Time (in days) belore d~composilion of lhe samples containing the stabiliser combina~ioll û.3 % DSTDP ~ (). I % compoun(l according to ~he invention an(l containing no stabiliser takcx phlce Number of days oven ageing before Stabilisers dccomposition tnkes place at 135C at 149C
none 1 d DSTDP+compoundNo. 8 126 50 DSmP-~compoundNo. 13 115 40 DSTDP + compoun:l No. 17 156 65 DSTDP+ compound No. 20 162 60 DSTDP+ compound No. 21 175 38 DSTDP~ compound No. 22 247 57 DSTDP ~ compound No. 23 245 85 DSTDP+ compound No. 24 140 43 DS'~DP + compolmd No. 25 121 24 DSTDP+ compound No. 26 151 33 DSTDP~compoundNo. 28 147 47 DSTDP+ compound No. 29 145 49 DSTDP+ compound No. 30 194 50 DSTDP~ compound No. 35 148 50 DSTDP ~ compound No. 36 190 71 DSTDP ~ compound No.52 158 55 DSTDP+ compound No. 53 158 48 DSTDP~ compound No. 54 161 55 DSTDP+ compound No. 55 150 43 DSTDP~ compound No. 56 170 52 I:)STDP + compound No 57 193 70 DSTDP-~ compoundNo 58 173 52 DSTDP + compound No 59 163 63 DSTDP + compound No 60 159 4~
Example 63: Stabilisation of acrYlonitrile-butadiene-styrene terpolymer (ABS3 The stabilisers indicated in Table 13 are dissolved in 40 ml of a mixture of hexane and isopropanol. The solution is added ~o a dispersion of 100 g of ABS in 600 ml of water, with vigorous stirring, after which the solution is completely absorbed by the ABS within about one minute. The polymer powder containing the stabilisers is then filtered off and dried for 40 hours at 40C under vacuum.

For comparison purposes, the subsequent processing steps are also carried out using~ a sample without stabilisers.

2 % of titanium dioxide, as pigment, and 1 % of ethylene-bis-stearic acid amide, as ~090082 - 4') -lubricant, are added to thc dry l)owdcr. The rni~ r~ is lhen compollnde(l within 4 minutes on a 2-roll mill al l X0C.

A plat~ ().8 mm thick is i r~s~d t`rom th~ rollc(l ~ cl al 175C and 45 x 17 mm2 les~
pieces are pllnchc(l lrolll this plat~. The te~t to determin~ th~ etfectiv~ncss of the added stabilisers is carr;e(l olll by heal al~in~ in a circul~ltill~ air oven at lX~)C. Thc criterion is the colour development ~ter a test tirne of 45 minules. The colour intensity is determined in accordance with ~STM D 1')25-70 (Yellowness Index) Tlle test results are summarised in Table 13. Higher figures indicate more intensive yellowing. The tests show that yellowing is ef~ectively suppressed by ~he compounds according to the invention.
able 13: Yellowness Index after 45 minute oven ageing of samples containing no stabilisers, 0.5 % of dilauryl thiodipropionate ~DLTDP) and also 0.5 %
DLTDP+0.25%of the indicated compound nccording to the inventio Stabilisers Yellowness Index after 45 Minutes at L80C
none 78 DLTDP+compoundNo.l 26 DLTDP+ compound No. 7 25 DLTDP+ compound No. 8 26 DLTDP+ compound No. 12 34 DLTDP+ compound No. 13 39 DLTDP+ compound No. 15 33 DLTDP+compoundNo.16 34 DLTDP+ compound No. 17 26 DLTDPt compound No. 19 31 DLTDP+ compound No. 20 26 DLTDP+ compound No. 21 33 DLTDP+ compound No. 22 21 DLTDP+ compound No. 23 29 DLTDP+ compound No. 24 32 DLTDP+ compound No. 25 41 DLTDP + compound No. 26 28 DLTDP+ compound No. 28 30 DLTDP+ compound No. 29 32 DLTDP+ compound No. 31 29 DLTDP+compound No. 32 27 DLTDP+ compound No. 33 32 DLTDP+ compound No. 34 30 DLTDP+compound No. 39 36 DLTDP+ compound No. 40 26 DLTDP+ compound No. 42 32 209~82 - s() -l~xample 64: _abi!is.lti_rl of X-S~R l~l x c~oxylated SBR latex) In ench case 0.25 parts by weight of ~he compoun(ls accor(lillg lo the inventiotl lisîed ;n Tablc l4 are dissolve(l in a little methanol and stirred into lO() par~s by weigllt of X-SBR
latex (styrene-butadienc copolymer). A precisely clefined nmount of latex is then filled into Petli dislles an(l dried in an oven at 80C. Transparetlt films havillg n layer thickness of about 0.2 mm are obtained. For comparison purposes, a sample without stabilisers is prepared.

The test to determine the elfectiveness of the added stabilisers is carried out by heat ageing in a circulating air oven at 135C. The discoloration ot the samples is deterrnined in accordance w;th ASTM D 1925-70 (Yellowness Index) after the intervals indicated in Table 14. The test results are surrlmarised in Table 14. Higher tlgures indicate more intensive yellowing. The tests show that yellowing is efFectively suppressed by the compounds according to the invention.

Table 14: Yellowness Index after the indicated ageing time at 135C

Yellowness Index after ageing time (in hours) Stabiliser 4 h 12 h 24 h 40 h none 92 * ~ *
0.25 % compound No. 31 46 52 64 75 0.25 % compoundNo. 32 40 46 58 69 *: not measurable (sample black)

Claims (20)

1. A compound of the formula I

, (I) in which n is an integer from the range from 4 to 8 and m is an integer from the range from 1 to 4;
if m = 1, A is C1-C25alkyl, which is unsubstituted or substituted by C5-C8cycloalkyl; or is C2-C25alkyl which is interrupted by C5-C8cycloalkyl or one or more groups selected from -S-, -O- and NR2-; or, if m = 1, A is C5-C8cycloalkyl, which is unsubstituted orsubstituted by C1-C12alkyl or C2-C12alkenyl; C6-C8cycloalkenyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl; phenyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl; naphthyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl; biphenyl, which is unsubstituted or substituted byC1-C12alkyl or C2-C12alkenyl; or C2-C25alkenyl; C6-C10bicycloalkenyl;
C7-C12phenylalkyl; C8-C12phenylalkenyl; C11-C16naphthylalkyl; C12-C16naphthylalkenyl;
C13-C18biphenylalkyl; C14-C18biphenylalkenyl; or a group of the formula II

(II);

if m = 2, A is a direct bond; C1-C12alkylene; C2-C12alkenylene; C5-C8cycloalkylene, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl;
C6-C8cycloalkenylene, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl; C6-C10bicycloalkenylene; phenylene; naphthylene; a divalent heterocyclic radical from the group comprising furan, thiophene or pyrrole, which is saturated on the nitrogen atom by hydrogen or the substituent -R2; or, if m = 2, A is C2-C36alkylene which is interrupted by C5-C8cycloalkylene or phenylene or one or more groups selected from -S-,-O- and -NR2-;
if m = 3, A is Cl-C8alkanetriyl; C2-C8alkenetriyl; benzenetriyl; naphthalenetriyl; a trivalent group of the formula ; or C2-C18alkanetriyl, which is interruptedby at least one of the groups -S-, -O- or NR2-;
or, if m=4, A is a benzene radical, naphthyl radical, tetrahydrofuryl radical or cyclohexyl radical having 4 free valencies;
R1 and R1, independently of one another, are C1-C24alkyl or C5-C8cycloalkyl;
R2 is H or C1-C4alkyl;
R3 and R4, independently of one another, are C1-C4alkyl; and R5, R6 and R7, independently of one another, are C1-C3alkylene.

2. A compound of the formula I according to claim 1, in which R1' has the meaning of secondary or tertiary C3-C24alkyl or C5-C8cycloalkyl; and R1 has the meaning C1-C10alkyl or C5-C8cycloalkyl.

3. A compound of the formula I according to claim 1, in which R1' has the meaning tert-butyl and R1 has the meaning methyl.

4. A compound of the formula Ia , (Ia) in which n is an integer from the range from 4 to 8 and m is an integer from the range from 1 to 3, if m=1,A is C1-C25alkyl, which is unsubstituted or substituted by C5-C8cycloalkyl, or is C2-C25alkyl, which is interrupted by C5-C8cycloalkyl or one or more groups selected from -S-, -O- and -NR2-, or, if m = 1, A is C5-C8cycloalkyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl, C6-C8cycloalkenyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkynyl, phenyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl, naphthyl, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl, biphenyl, which is unsubstituted or substituted byC1-C12alkyl or C2-C12alkenyl, or A is C2-C25, C6-C10bicycloalkenyl, C7-C12phenylalkyl, C8-C12phenylalkenyl, C11-C16naphthylalkyl, C12-C16naphthylalkenyl, C13-C18biphenylalkyl, C14-C18biphenylalkenyl, or a group of the formula II
(II), if m = 2, A is a direct bond, C1-C12alkylene, C2-C12alkenylene, C5-C8cycloalkylene, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl, or A is C6-C8cycloalkenylene, which is unsubstituted or substituted by C1-C12alkyl or C2-C12alkenyl, or A is C6-C10bicloalkenylene, phenylene, naphthylene or C2-C18alkylene which is interrupted by C5-C8cycloalkylene or phenylene or one or more groups selected from -S-, -O-, and NR2-, if m = 3, A is C1-C8alkanetriyl, C2-C8alkenetriyl, benzenetriyl, naphthalenetriyl, a trivalent group of the formula , or C2-C18alkanetriyl which is interrupted by one or more groups selected from -S-, -O- and NR2-, R1 is methyl or tert-butyl, R2 is H or C1-C4alkyl, R3 and R4, independently of one another, are C1-C4alkyl, and R5, R6 and R7, independently of one another, are C1-C3alkylene.

5. A compound of the formula I according to claim 1, in which if m = 1, A is C1-C25alkyl, which is unsubstituted or substituted by C5-C8cycloalkyl; or C2-C25alkyl, which is interrupted by C5-C8cycloalkyl, which is unsubstituted or substituted by C1-C12alkyl;
if m = 1, A is C5-C8cycloalkyl, which is unsubstituted or substituted by C1-C12alkyl;
C6-C8cycloalkenyl, which is unsubstituted or substituted by C1-C12alkyl; phenyl, which is unsubstituted or substituted by C1-C12alkyl; or C2-C25alkenyl; C7-C12phenylalkyl; or a group or the formula II

if m = 2, A is a direct bond; C1-C12alkylene; C2-C12alkenylene; C5-C8cycloalkylene, which is unsubstituted or substituted by C1-C12alkyl; C6-C8cycloalkenylene, which is unsubstituted or substituted by C1-C12alkyl; phenylene; a divalent heterocyclic radical from the group comprising furan, thiophene or pyrrole, which is saturated on the nitrogen atom by hydrogen or the substituent -R2; or, if m = 2, A is C2-C18alkylene which is interrupted by C5-C8cycloalkylene or phenylene or one or more groups selected from -S-, -O- and -NR2-; and if m = 3, A is C1-C8alkanetriyl; C2-C8alkenetriyl; benzenetriyl; a trivalent group of the formula ; or C2-C18alkanetriyl, which is interrupted by one or more groups selected from -S-, -O- and -NR2-; and if m = 4, A is a benzene or cyclohexyl radical having 4 free valencies.

6. A compound of the formula I according to claim 1, in which R1 is tert-butyl or cyclohexyl and R1 is methyl, tert-butyl or cyclohexyl;
n is a number from the range 4 to 6; and if m = 1, A is C6-C18alkyl or C2-C12alkenyl;
if m = 2, A is a direct bond; C1-C12alkylene; phenylene; ; or C2-C36alkylene interrupted by 1 to 5 oxygen or sulfur atoms;
if m = 3, A is benzenetriyl or a trivalent group of the formula ; and if m = 4, A is a benzene radical having 4 free valencies.

7. A compound of the formula I according to claim 1, in which n is an integer from the range from 5 to 8.

8. A compound of the formula I according to claim 1, in which n is an integer from the range from 6 to 8.

9. A compound of the formula I according to claim 6, in which m is 1 or 2.

10. A compound of the formula 1 according to Claim 9, of the formula in which A is -(CH2)j-; -(CH2)k-S-(CH2)k-; or -(CH2)2-O-[(CH2)2-O-]j-(CH2)2-; j is 0 or an integer from the range from 1 to 4; and k is an integer from the range from 1 to 3.

11. One of the compounds (a) to (l) a) 6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl stearate;
b) 6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexyl stearate;
c) bis[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] succinate;
d) bis[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] aldipate;
e) bis[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] suberate;
f) bis[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] isophthalate;
g) bis[6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexyl] isophthalate;
h) tris[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] trimellitate;
j) tris[6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexyl] trimellitate;
k) tris[6-(3-tert-butyl-4-hydroxy-5-methylphenyl)hexyl] trimesate; and 1) tris[6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexyl] trimesate according to claim 1.

12. A compound of the formula III

, (III) wherein Gl und Gl, independently of one another, are C1-C24alkyl or C5-C8cycloalkyl, the meaning tert-butyl being excluded for G1, and n is an integer from the range from 4 to 8.

13. A compound according to claim 12, in which G1' is tert-butyl or cyclohexyl and C1 is methyl or cyclohexyl.

14. A composition containing an organic material sensitive to thermal, oxidative and/or actinic degradation and an effective stabilising amount of a compound of the formula I
according to claim 1.

15. A composition according to claim 14, in which the organic material is a synthetic organic polymer or mixture of such polymers.

16, A composition according to claim 15, in which the synthetic organic polymer is a polyolefin or a styrene copolymer.

17. A composition according to claim 15, in which the synthetic organic polymer is sensitive to oxidative degradation.

18. A method for stabilising organic material against thermal, oxidative or/and actinic degradation, which method comprises adding an effective stabilising amount of a compound of the formula I according to claim 1 to said material.

19. A composition containing an organic material sensitive to thermal, oxidative or/and actinic degradation and an effective stabilising amount of a compound of the formula IV
, (IV) in which n is an integer from the range from 4 to 8 and R1 and R1', independently of one another, are C1-C24alkyl or C5-C8cycloalkyl.

20. A method for stabilising organic material against thermal, oxidative or/and actinic degradation, which method comprised adding an effective stabilising amount of a compound of the formula IV according to claim 19 to said material.