CA2001241A1

CA2001241A1 - Phenol group-containing compounds as anti-oxidants in organic materials

Info

Publication number: CA2001241A1
Application number: CA002001241A
Authority: CA
Inventors: Samuel Evans
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1988-10-25
Filing date: 1989-10-23
Publication date: 1990-04-25
Also published as: MX18065A; AU630631B2; KR900006482A; ZA898041B; DE58903802D1; DD288830A5; ES2051958T3; AU4363289A; EP0366040B1; EP0366040A1; JPH02209843A; BR8905444A; RU1826989C

Abstract

A-17278/+

Phenol group-containing compounds as anti-oxidants in organic materials Abstract Compositions containing a) an organic material subject to oxidative, thermal or actinic degradation and b) compounds of general formula I

(I), wherein, for example, R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, and R3 is -H or CH3, and n is a number from 1 to 4 or 6, and, when n is 1, A is -OR4 or , and, for example, R4 is -H, alkyl having from 1 to 45 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms or alkenyl having from 2 to 18 carbon atoms, and each of R5 and R6, independently of the other, is -H, alkyl having from 1 to 20 carbon atoms, phenyl or cycloalkyl having from 5 to 12 carbon atoms, or, when n is 2, for example A is -O-CxH2x-O-, -O-(CH2CH2O)aCH2CH2O-, -O-CH2-CH2-B-CH2CH2O-, , , , -O-CH2CH=CHCH2-O-, -O-CH2C=CCH2-O-, or wherein a is a number from 1 to 30, x is a number from 2 to 20, B is, for example, -S-, and R7 and R8 are as defined above and b1 is a number from 2 to 10, or, when n is 3, A is , or, when n is 4, A is , or or, when n is 6, A is

Description

':'`

A-17278/~

Phenol ~roup-containing compounds as anti-oxidants in or~anic materials The present invention relates to novel compositions containing organic materials subject to oxidative, thermal or actinic degradation and hydroxyphenylcarboxylic acid ester compounds, to novel hydroxyphenyl-carboxylic acid compounds and to their use as anti-oxidants.

The stabilisation, for example, of lubricants or plastics with anti-oxidants of the hydroxyphenylcarboxylic acid ester series is known from US-A-3 247 240; US-A-3 644 482; US-A-3 962 123; US-A-3 984 460 and US-A-3 494 887.

DE-A-28 37 141 discloses a lubricating oil formulation consisting of a petroleum distillate, small proportions of other substances and an anti-oxidant, the anti-oxidant containing the ~,~-alkanediol bis-ester of a 2,4,6-trialkylphenolcarboxylic acid.

US-A-4 529 809 describes a process for the preparation of hydroxyphenyl-carboxylic acid esters, wherein methyl, ethyl and propyl esters of 2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionic acid act as important intermediates in the manufacture of anti-oxidants for poly-propylene resins of the pentaerythritol-tetrakis-[2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate] type.

Surprisingly, a number of compounds has now been found which exhibit improved properties as anti-oxidants in organic materials, especially in functional fluids and plastics.

: -.` : . `' ' . ,":. . :

~` , ` `` '` ~ ~ : '.

The present invention relates to compositions containing a) at least one organic material subject to oxidative, thermal or actinic degradation and b) at least one compound of general formula I

H0 ~ ~3 R2 ~ CH2-CH-~ ~ A (I), wXerein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, and R3 is -H or CH3, and n is a number from 1 to 4 or 6, and, when n is 1 A is -oR4 or -~ and R4 is -H alkyl \R~
having from 1 to 45 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 2 to 18 carbon atoms, C~3/CH3 C~3 CH3 or -CHzCHz-XR , and each of Rs and R5, independently of the other, is -H, alkyl having from 1 to 20 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, aralkyl having from 7 to 10 carbon atoms or C~3/CH3 _.\ ~ -R9 . _ .
C~3 CH3 ,,,... , ;

:: :: ~ : , : ~ , ~ , , ~ . , , ,,: .

- 3 ~

and, in addition, Rs is -NH2, R9 is -H, alkyl having from 1 to 8 carbon atoms, -~-Rl, -O or -OR9', wherein R9' is -H, alkyl having from 6a 1 to 25 carbon atoms or -~-Rl, X is -o-, -s- or -~- , R is -~}I-~H-C-OR , \ _ /
~ ~2 -H, alkyl having from 1 to 24 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms or -CHz-lCl-ORb, and R10 is alkyl having from 1 to 20 carbon atoms, R is -H or -CH3, R is -H or alkyl having from 1 to 24 carbon atoms and Rc is -H or -CH3, with the proviso that Ra and Rc are not -CH3 at the same time, and R is alkyl having from 1 to 18 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 24 carbon atoms, or Cs-C3cycloalkyl, or, when n is 2, A is -O-C H2 ~~~ -O-(CH2CHzO~ CHzCHzO-, -O-CH2-CH2-~-CH2-CH2-O-, C~3/CH3 CH3/CH3 C~3/CH3 -O--\ /N-(CH2)z-O- , -O--\ /N-CHzCH=CH-CHz-N\ /--O- , C~3 CH3 C~3 CH3 C~3 CH3 C~3/CH3 CH\3~CH3 -O--\ /N-(CH2)blN\ /--O- , C~; CH3 CH3 CH3 -O-CH2CH=CHCI12-O-, -o-cH2c=ccH2-o-~ -o-cH2cH2NH-c-c-NH-cH2cH2 ÇH3 -O-CH2-CH2-O--~ ~-~¢~-~ ~--O-CH2-CHz-O-, ~ .
- ~ ÇH3~ \. or- ~(CH2)b2 ::~ . , . :: ..
:: .
'. , , . : ~,., :, . ~:
.,: : ;: .

- 2q~

wherein a is a number from 1 to 30, x is a number from 2 to 20, B is -S- , -~- or -S-~-S- , RA is alkyl having from 1 to 20 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 20 carbon atoms, cyclohexyl or CH3\ /CH3 CH~ CH3 and each of R11, R12 and R13, independently of the others, is -H, alkyl having from 1 to 12 carbon atoms or phenyl, or R12 and R13 together with the carbon atom to which they are bonded form a cycloalkyl ring having from S to 12 carbon atoms, b1 is a number from 2 to 10 and 2 is a number ÇH2CH20-from 0 to 6, or, when n is 3, A is -OCHzCHz-X~CH2CH2O~ or -O-CH2- H-CH2-O-, or, when n is 4, A is 1/_ \. or 1/_~, or, when n is 6, A is CIHz--O--O - - CHz-~-CHzO-If R1, R2 and R are, for example, alkyl having from 1 to 18 carbon atoms, then the alkyl group can be straight-chain or branched and can be, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, .. , ~ ~:
- : , 1-methylheptyl, 1,1,3-trimethylhexyl or 1-methylundecyl. Alkyl having from 1 to 12 carbon atoms is preferred, and alkyl having from 1 to 8 carbon atoms is especially preferred.

Eor R1 and R2, those alkyl groups from the above ].ist of examples which have from 1 to ô carbon atoms are to be regarded as advantageous and those having from 1 to 4 carbon atoms are to be regarded as preferred.
The tert.-butyl group is especially preferred for R1 and R2.

R4 is, for example, straight-chain or branched alkyl having from 1 to 45 carbon atoms. Examples thereof are those indicated for R1 and R2 and also eicosyl, hemicosyl, docosyl, triacontyl, etc. Preferably, R9 as alkyl is C1-C20alkyl, especially C1-C1~alkyl.

RA, R5, Rs and R10 can be alkyl having from 1 to 20 carbon atoms, straight-chain or branched alkyl groups being intended and reference being made to the above list of examples for R1 and R2, supplemented by the further example of eicosyl. Alkyl groups having from 1 to 12 carbon atoms are preferred.

R9 or R9' is, for example, alkyl having from 1 to 8 carbon atoms, the alkyl groups being straight-chain or branched and being methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2-ethylbutyl, isoamyl, 1-methyl-pentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, l-methylhexyl, iso-heptyl or l-methylheptyl.

An advantageous radical for R9 is alkyl having from 1 to 4 carbon atoms and accordingly is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tert.-butyl.

If R or R5a is an alkyl group having from 1 to 24 carbon atoms, then these include the straight-chain or branched alkyl groups as indicated as examples of R1, supplemented, for example, by eicosyl or docosyl. Alkyl groups having from ] to 18 carbon atoms are preferred.

:~ : .............................. , , : , . . . .
~, , . , : . .

.

R11, R12 and Rl3 are, for example, independently of one another, alkyl having from 1 to 12 carbon atoms, the alkyl groups being straight-chain or branched and there being mentioned by way of example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetra-methylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethyl-hexyl or 1-methylundecyl. The corresponding examples having from 1 to 8 carbon atoms are preferred.

R , and Rs and R6, independently of one another, can advantageously bealkyl having from 1 to 12 carbon atoms. The alkyl group can be straight-chain or branched and examples can be taken from the corresponding list for R11 and R1 2 above.

Preferably, RA can be a C4-C8alkyl group and examples of such a group are n-butyl, isobutyl, tert.-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl or 1-methylheptyl.

Where isoCgH17 is mentioned, it may be understood as including also a mixture of isomers.

If R1, R2, R4, Rs, Rs or R5a is cycloalkyl having from 5 to 12 carbon atoms, then this includes, for example, cyclopentyl, cyclohexyl, cyclo-heptyl, cyclooctyl, cyclodecyl and cyclododecyl. Cyclohexyl is preferred.

R6a as cycloalkyl having from 5 to 8 carbon atoms can be cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Furthermore, Rs and R6 are also C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms. Preferred are cycloalkyl having from 5 to 12 carbon atoms and are substituted by one, two or three C1-C4alkyl groups. Examples thereof are 2- or 4-methylcyclohexyl, dimethylcyclo-hexyl, trimethylcyclohexyl or tert.-butylcyclohexyl.

:, '- ' ' ' ~ ' ' If R is phenyl substituted by one or more, preferably one, two or three, alkyl groups having a total of from 1 to 24 carbon atoms or RA is phenyl substituted by one or more, preferably one, two or three, alkyl groups having a total of from 1 to 20 carbon atoms, then examples of substituents R a and RA may include methylphenyl, dimethylphenyl, tri-methylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert.-butyl-phenyl, di-tert.-butylphenyl, methyl di-tert.-butylphenyl, tert.-octyl-phenyl and di-tert.-octylphenyl.

Finally, R12 and R1 3 can form together with the carbon atom to which they are bonded a cycloalkyl ring having from 5 to 12 carbon atoms. Examples that may be mentioned are a cyclopentyl, cyclohexyl, cycloheptyl, cyclo-octyl, cyclodecyl or cyclododecyl ring. A cyclohexyl ring is preferred.

If R1, R2, Rs or Rs is aralkyl having from 7 to 9 carbon atoms or from 7 to lO carbon atoms, then examples thereof are benzyl, phenethyl, ~-methylbenzyl or ~,~-dimethylbenzyl. Benzyl is preferred.

If R4 is an alkenyl group having from 2 to lô carbon atoms, then examples thereof are vinyl, propenyl, allyl, butenyl, methallyl, hexenyl, decenyl or heptadecenyl.

/Rs The radical -N\ can also be a hydrazine radical of formula -NH-NH2, which may include the hydrazine hydrate radical.

For Rs or Rs as alkenyl having from 3 to 8 carbon atoms there come intoconsideration, for example, allyl, 2-methallyl, 2-butenyl or 2-hexenyl.

Compounds of formula I wherein n is 1 or 2 are preferred.

Advantageous compositions according to the invention contain at least one compound of formula I wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, and R3 is -H, and n is a number from 1 to 4 or 6, wherein, when n is 1, A is -oR4 or -N\ , and R4 is -H, alkyl havlng from 1 to 20 carbon atoms, cyclohexyl, alkenyl having from 2 to 18 carbon atoms or -CH2CH2-XR , and Rs is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, benzyl or -NHz, and Rs is -H or alkyl having from 1 to 12 carbon atoms, X is -O-, -S- or -~-, R5a is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl or ~Rl -CHz-~ -OH
\R2 and R6a is alkyl having from 1 to 12 carbon atoms, phenyl, or phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH20)aCHzCH20-, -O-CH2-CH2-B-CH2-CH2-O-, H3C\ /CX3 H3C\ /CH3 -0--~ ~N-(CH2)bl-N~ ~---O--O-CHzCH=CHCH2-O-, -O-CHzCH2NH-ICl-lCl-NH-CH2CH2-O-, -O-CH2-CH2-O--~ ~--¢--~ ~--O-CH2-CHz-O- , -0-~ --0- , \ I /- or - ~(CH2)b2-.

~9~4~.

wherein a is a number from 1 to 12, x is a number from 2 to 12, ~ is -S- or -~- , RA is alkyl having from 1 to 12 carbon A

atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms or cyclohexyl, and R11 is ~H, alkyl having from 1 to 12 carbon atoms or phenyl, and b1 is a number from 2 to 6 and b2 is a number from O to 6, or, when n is 3, A is ,CHZcH20--OCHzCHz-~-CHzCHzO- or -O-CHz-CH-CHz-O-, or, when n is 4, A is -O--o ~ \. --T/~
-o o-or, when n is 6, A is CIHz--O--O - - CHz-~-CHzO-CHz-O- 2 Especially advantageous compositions contain at least one compound of formula I wherein R1 is alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, R2 is -H, alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, and R3 is -H, and n is 1 and A is -oR4 or - ~\ , wherein R4 is -H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, -CHzCH=CH2, -(CHz)7-CH=CH-(CH2)7CH3, H3C\ /CH3 ~ -R9 or -CHzCH2XR , wherein R9 is -H, alkyl having from 1 to 4 carbon atoms, -O , ~O-alkyl having from 1 to 4 carbon atoms or cyclohexyl, X is -O-, , ;, 6a -S- or -~- , R is -H, alkyl having from 1 to 18 carbon atoms, phenyl, -CHz-C-OR, ~Rl - ~H ~H ~-ORb or -CH2--~ ~ -OH

wherein Rb is alkyl having from 1 to 24 carbon atoms, Ra is -H or -CH3, Rc is -H and R6 is alkyl having from 1 to 12 carbon atoms or phenyl, and each of Rs and R6, independently of the other, is -H, alkyl having from 1 to 12 carbon atoms, phenyl or H3C\ /CH3 --\ /N-R9 wherein R9 is as defined above, or Rs is -NH2 and R6 is -H, or n is 2, in which case A is --CxH2x-- and x is 2 to 8-Preferred compositions contain at least one compound of formula I whereinR1 is tert.-butyl, R2 is -H, methyl or tert.-butyl, and R3 is -H, and n is 1, in which case A is - oR4 or -N\ , and R4 is:alkyl having from l to 18 carbon atoms, -(CH2)7-CH=CH-(CH2)7CH3, H3C\ /CH3 --\ /N-(H,CH3) or -CH2CH2-SR5a wherein R5a is -H or -CH2-CHz-~-O-R , wherein R is n-C4Hg to n-CgH17 or tert.-C4Hg to tert.-CaH17, or n is 2, in which case A is -O-C H2 ~~ and x is 2 to 8, or A is -O-(CH2-CN2-O-) -CH2-CHz-O- and a is 1 to 4, or A is .

. ' ~ .

-~" 2~

-O-CHz-CHz-B-CH2-CH2-O- and B is -S- , -~- or -S-~-S- , wherein RA is C4-Cgalkyl or phenyl, R12 is H or C1-Cgalkyl and R13 is H, C1-Cz-alkyl or phenyl, or A is H3C\ /CH3 H3C\ /CH3 H3C\ /CH3 -o--\ /N-(CHz)2-O- . ---\ /N-CHzCH=CH-CHz-N\ /--0- or H3C\ /CH3 H3C\ /CH3 -0--\ /N-(CHz)b1N\ /--0-wherein _1 is 2 to 6, or A is -O-CH2-CH=CH-CH2-O-, -O-CH2-C--C-CH2-O-, \ I /~ , -O-CH2-CH2-NH-~-ICl-NH-CHz-CH2-O- or - ~(CHz)b-2~--wherein 2 is O to 6 and R11 is -H or C1-Cgalkyl.

Further preferred compositions contain at least one compound of ~ormula I
wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, and R3 is -H
and n is l and A is -oR4 and R4 is C1-C1galkyl.

Further preferred compositions include those containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, and R3 is -H, and n is 2 and A is -O-C H2 ~~ and _ is 2 to 6, or A is -O-(CHz-CHz-O) -CH2-CH2-O- and a is l, 2 or 3, or A is -O-CHz-CHz-B-CH2-CHz-O- and B is -S- or -~-, .~ \. .

, ~ ,; .. . . ' :
` ', . ................... .

f~

or A is -O-CH2-CH2-NH-~-~-NH-CHz-cH2-o- or A is -NH-NH-.

Also preferred is a composition containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, R3 is -H, n is 1 and A is -oR4, wherein R4 is C1-C1aalkyl, or n is 2 and A is -O-CxH2 -O-, and x is 2 to 6, -OCHzCH2--S-CH2CH20- or -o(CH2CH20) CH2CH2-O- and a is 1 to 4.

A composition of the above-mentioned type containing at least one com-pound of formula I wherein a is 1 or 2 is especially preferred.

Also preferred is a composition containing at least one compound oE
formula I wherein R1 is tert.-butyl, R2 is -H, - CH3, tert.-butyl, and R3 ÇH2 -CH2 -o_ is -H and n is 3 and A is -O-CH2CH2-N-CH2-CH2-O-, or n is 4 and A is -o-l/o\.
\!_.

or n is 6 and A is IcH2-o-O - - CH2-~-CHzO-H2-o- 2 Particularly preferred are compositions containing at least one compound from the series of formulae IC(CH3)3 \ . ~ \ .
(H3C)3C/ ~-/ \CHzCH-ICl-o-cHz-cH2 - S

:

~ ~(CH3)3 (H3C)3C ~ CH2CH-~-O-CH2-CHz - - O

Cl(CH3)3 (H3C)3C ~-/ \CH2CH-C-oR4 wherein R4 is C1-C18alkyl and especially CH3, -n-C4Hg, -isoCgH1 7 -n-C12H2s or -n-C1sH3 7, Cl(CH3~3 IC(CH3)3 HO\ ~ -\ /OH
I iI c, H3 ,CH3 ! i1 and (H3C)3C i- CH2-~H-~-O-(CH2)6-O-~-CH-C~2 C(CH3)3 ~(CH3)3 \.~ \.
(H3C)3C ~-/ \CH2-CH-~-O-CH2-CH2- _ N~

The above-mentioned individual compounds in lubricants of the group con-sisting of mineral oils, synthetic oils or mixtures thereof represent particularly valuable compositions.
, The compounds of formula I can be prepared, for example, by a Michael addition, the reaction following the equation below:

~ -- \ 4 t~t ~30_tBU / -- \

wherein R1, R2, R3 and R4 can be as defined above.

.

~ ~.. ' " ' ~'' :`' ,~
`:.

The process is carried out by reacting the alkyl-substituted phenol with the olefinic ester in stoichiometric excess in the presence of a cata-lytic amount of a base, for example a quaternary ammonium base, an alkali metal amide or an alkali metal alkanolate, at a temperature of from 150 to 220C.

A detailed description of the process can be found, for example, in US-PS 4 529 809 which is mentioned at the beginning.

A further process for the preparation of compounds according to the invention is the transesterification that follows the general equation:
~ _ /R3 CH3 n HO~ -CH2-CH-~-o-R4 + A'-(H) ~ OH~ -CR2- R-C ~ ' I n R4OR

wherein Rl, R2 and R3 are as defined above, while A' has the same meaning as A with the exception of the radical -NRsRs. There are advantageous]y used starting esters in which R4 is Ci-C4alkyl, especially methyl, which, as described above, can likewise be prepared by reaction of a correspond-ing phenol with a methacrylate of formula Cl H 3 H2C= -ICl-OR1 , wherein Rl is C1-C4alkyl.

Suitable catalysts are, for example, dibutyltin oxide Ti(-O-isoC3H7)4, LiNHz, LiH, LiOH, KOR, NaOR, LiOR wherein R is H or C1-5loalkyl~ or : ' :
.

:' ' " " ''':

R'\
H0~ --R"' , . = .

wherein each of R', R" and R"', independently of the others, is H or alkyl having from l to 10 carbon atoms.

The process is advantageously carried out in a solvent, such as benzene, toluene, xylene, dimethylformamide etc.

A further process for the preparation of compounds according to the invention follows the general equation for the esterification:

n H0 ~ CHz H COzH + A'-(H) ~ H0- ~ ~ -CH2- H- C~A'~ o R~ acid as R2/
catalyst . n wherein Rl, R2, R3 and A' can be as defined above. The reaction is carried out in the presence of an acid as catalyst. Suitable catalysts are, for example, fuller's earth, such as Tosil L80S, or p-toluenesul-fonic acid. The preparation of the carboxylic acid starting compounds can be effected by hydrolysis of compounds of formula Rl ,R3 H0~ CH2-CH - ~C-oR4 R~

A process that is also suitable for the preparation of compounds in accordance with the present invention is also the reaction oE a corre-sponding acid chloride with an alcohol or amine. The procoss can be described more accurately using the following reaction equation:

-:. . ' ' ~ . '. .'' ' : . : : ' , ,. ,. .:

- 2~

n HO~ -CH2-CH- ~Cl + A(H) - ~ HO-~ -CH2-CH- ~A + n HCl .=. acid =-R~ acceptor R~ n The meanings of R1, R2, R3 and A are given above. As acid acceptor there may be used, for example, pyridine, triethylamine or an alkali metal hydroxide, such as NaOH or KOH.

Another process for the preparation of compounds in accordance with thepresent invention follows the equation:
~ 1 HO ~ R3 ~1 R2/ \-~ \CH2-8H-~-OR + R'N\ ______~ HO ~ R3 /Rs R2 ~ CH2-~H-~-N\ ~ ROR' wherein R and R' have, for example, independently of one another9 the same meaning as R1 or are hydrogen. The reaction is effected by thermal reaction at, for example, 80-190C.

The compounds of formula I of the invention are excellently suitable for stabilising organic material, especially organic material that is sensi-tive to oxidative, thermal or actinic degradation.

The present invention therefore relates to compositions containing organic materials that are sensitive to oxidative, thermal or actinic degradation and at least one compound of formula I, and to the use of compounds of formula I for stabilising organic materials that are sensi-tive to oxidative, thermal or actinic degradation.

Advantageously the organic materials contain 0.01 to 10, for example, 0.05 to 5, preferably 0.05 to 3, especially 0.1 to 2 % by weight, based on the organic material, of compounds of formula I.

, , ' .2(~
-- 1 7 ~

The invention relates also to compositions that contain an organic material that is sensitive to oxidative, thermal or actinic degradation and especially a synthetic polymer or a functional fluid and at least one compound of formula I.

Further organic materials that can be stabilised according to the inven-tion with the aid of the compound of formula I are, for example:

1. Polymers of mono- and di-olefins, for example polypropylene, polyiso-butylene, polybutene-l, polymethylpentene-l, polyisoprene or polybuta-diene, and polymers of cycloolefins, for example of cyclopentene or nor-bornene; also polyethylene (which can optionally be cross-linked), for example high density polyethylene ~HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).

2. Mixtures of the polymers mentioned under 1., for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differen~ types of polyethylene (for example LDPE/HDPE).

3. Copolymers of mono- and di-olefins with one another or with other vinyl monomers, for example sthylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density poly-ethylene (LDPE), propylene/butene-l copolymers, propylene/isobutylene copolymers, ethylene/butene-l 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 or ethylene/acrylic acid copolymers and salts thereof (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene also mixtures of such copolymers with one another and with polymers mentioned under 1., for example polypropylene-ethylene/propylene copolymers, .; , .' ' ' ':
,,' ' ~
'` ' LDPE-ethylene/v nyl acetate copolymers, LDPE-ethylene/acrylic acid copolymers, LLDPE-ethylene/vinyl acetate copolymers and LLDPE-ethylene/acrylic acid copolymers.

3a. Hydrocarbon resins (for example Cs-C9) including hydrogenated modi-fications thereof (for example tackifier resins).

4. Polystyrene, poly-(p-methylstyrene), poly-(~-methylstyrene).

5. Copolymers of styrene or ~-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/maleic acid anhydride, styrene/acryonitrile/methacrylate; high-impact-strength mixtures consisting of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro-pylene/diene terpolymer; and block copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene, or styrene/ethylene-propylene/styrene.

6. Graft copolymers of styrene or ~-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene/styrene or polybutadiene/acrylo-nitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on poly-butadiene; styrene and maleic acid anhydride on polybutadiene; styrene, acrylonitrile and maleic acid anhydride or maleic acid imide on poly-butadiene; styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, and mixtures thereof with the copolymers mentioned under 5., as known, for example, as so-called ABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, for example polychloroprene, chloro-caoutchouc, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homopolymers and copolymers, especially polymers of halogen-containing ' .~ . .

- l 9 -vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloridelvinyl acetate.

8. Polymers derived from ~,~-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and poly-acrylonitriles.

9. Copolymers of the monomers mentioned under 8. with one another or with other unsaturated monomers, for example acrylonitrile/butadiene copoly-mers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinyl halide copolymers or acrylo-nitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinylbutyral, polyallyl phthalate, poly-allylmelamine; and copolymers thereof with olefins mentioned under point 1.

11. Homo- and co-polymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene, and those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modi-fied with thermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

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

, !, '' ', " , ~.

, ' 15. Polyamides and copolyamides 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, 6/9, 6/12, 4l6, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylene, diamine and adipic acid polyamides prepared from hexamethylenediamine and iso- and/or tere-phthalic acid and optionally an elastomer as modi-fier, for example poly-2,4,4-trimethylhexamethyleneterephthalamide, poly-m-phenylene-isophthalamide. Block copolymers of the above-mentioned poly-amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Also poly-amides or copolyamides modified with EPDM or ABS; and polyamides con-densed during processing ("RIM polyamide systems").

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

17. Polyesters derived from dicarboxylic acids and di-alcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as poly-ethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, polyhydroxybenzoates, and block polyether esters derived from polyethers with terminal hydroxy groups; also poly-esters modified with polycarbonates or MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Cross-linked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

21. Drying and non-drying alkyd resins.

.~ :

22. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyvalent alcohols, and vinyl compounds as cross-linking agents, and also their halogen-containing, difficultly combustible modifications.

23. Cross-linkable acrylic resins derived from substituted acrylic acid esters, for example from epoxy acrylates, urethane acrylates or polyester acrylates.

24. Allcyd resins, polyester resins and acrylate resins cross-linked with melamine resins, urea resins, polyisocyanates or epoxy resins.

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

26. Natural polymers, such as cellulose, natural rubber, gelatine and the polymer-homologously chemically modifiad derivatives thereof, such as cellulose acetates, propionates and butyrates, and the cellulose ethers, such as methylcellulose; and also colophonium resins and derivatives.

27. Mixtures (polyblends) of the above-mentioned polymers, for example PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVCIMBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylcltes, POM/thermoplastic PU~, PClthermoplastic P~R, POMlacrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

28. Natural and synthetic organic substances that are pure monomeric compounds or mixtures thereof, for example mineral oils, animal or vegetable fats, oils and waxes, or oils5 waxes and fats based on synthetic esters (for example phthalates, adipates, phosphates or tri-mellitates), and also mixtures of synthetic esters with mineral oils in any desired weight ratios, for example as used as functional fluids or as spinning preparations, including the aqueous emulsions of spinning pre-parations.

- . .

: , :
,,, ~ .

.
., 2q~

29. Aqueous emulsions of natural or synthetic rubbers, for example natural latex rubber or latices of carboxylated styrene-butadiene copoly-mers.

Advantageous groups are the synthetic polymers, and preferred groups ofplastics are those of the group consisting of the polyolefins, the elastomers, ABS, IPS, the polycarbonates, the polyimides, the polyesters, the polyacetals and the carboxylated S~R.

The incorporation of the stabiliser substances of the invention and, where applicable, of other additives into the organic material is effected according to known methods. For example, it can be effected by mixing in the products of the invention and, where applicable, other additives by the methods customary in the art before or during shaping, or alternatively by applying the dissolved or dispersed compounds to the polymer, where applicable with subsequent evaporation of the solvent. The products according to the invention can also be added to the materials to be stabilised in the form of a master batch which contains the products according to the invention, for example, in a concentration of from 2.5 to 25 % by weight. The products according to the invention can also be added before or during polymerisation or before cross-linking.

Advantageously, the incorporation of the compounds of formula I can be effected by the following methods:
- as an emulsion or dispersion (for example to latices or emulsion polymers), - as a dry mixture during the mixing of additional components or polymer mixtures, - direct addition into the processing apparatus (for example extruder, kneader etc.), - as a solution or melt.

The materials thus stabilised can be used in a great variety of forms, for example in the form of films, fibres, ribbons, moulding compositions, profiles or as binders for lacquers, adhesives or cements.

, `
~.

~ `

For example, in polyolefins the compounds of formula I exhibit extraor-dinarily good colour-enhancing properties.

In addition to the compounds of formula I, the above-mentioned organic materials and especially the synthetic polymers may also contain other additives. Examples of additional additives are:

1. Anti-oxidants 1.1. Alkylated monophenols, for example 2,6-di-tert.-butylpheno~, 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-(~-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methyl-phenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert.-butyl-4-methoxymethyl-phenol, 2,6-dinonyl-4-methylphenol.

1.2. Alkylated hydroquinones, for sxample 2,6-di-tert.-butyl-4-methoxy-phenol, 2,5-di-tert.-butylhydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated 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).

1.4. Alkylidene-bisphenols, 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-(-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-(~-methylbenzyl)--4-nonyl-phenol], 2,2'-methylene-bis-[6-(~,~-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)-4-methylphenol, 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrate], bis-(3-tert.-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, bis-[2-(3'-tert.-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert.-butyl-4 methylphenyl]-terephthalate.

1.5. Benzyl compounds, for example 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-sulfide, 3,5-di-tert.-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester, bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-iso-cyanurate, 1,3,5-tris-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-iso-cyanurate, 3,5-di-tert.-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, Ca salt of 3,5-di-tert.-butyl-4-hydroxybenzylphosphonic acid mono-ethyl ester, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurate.

1.6. Acylaminophenols, for example 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-(octylmercapto)-6-(3,5-di-tert.-butyl-4-hydroxyanilino)-s-triazine, N-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-carbamic acid octyl ester.

1.7. Esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with mono- or poly-valent alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)-iso-cyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide.

1.8. Esters of ~-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or poly-valent alcohols, for example with methanol, octa-decanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy-ethyl)-isocyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide.

1.9. Esters of ~-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid with mono- or poly-valent alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)-iso-cyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide.

1.10. Amides of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, for example N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-trimethylenediamine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxy-phenylpropionyl)-hydrazine.

2. UV absorbers and li~ht stabilisin~ a~ents 2.1. 2-(2'-hydroxyphenyl)-benzotriazoles, for example the 5'-methyl, 3',5'-di-tert.-butyl, 5'-tert.-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert.-butyl, 5-chloro-3'-tert.-butyl-5'-methyl, 3'-sec.-butyl-5'-tert.-butyl, 4'-octyloxy, 3',5'-di-tert.-amyl, 3',5'-bis-(~,~-dimethylbenzyl) derivative.

2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.

2.3. ~sters of unsubstituted or substituted benzoic_acids, for example 4-tert.-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol, 3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.-butyl-phenyl ester, 3,5-di-tert.-butyl-4-hydroxybenzoic acid hexadecyl ester.

Q ~y~ , for example ~-cyano-~,~-diphenylacrylic acid ethyl ester or isooctyl ester, ~-methoxycarbonylcinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxycinnamic acid methyl ester or butyl ester, ~-methoxy-carbonyl-p-methoxycinnamic acid methyl ester, N-(~-methoxycarbonyl-~-cyanovinyl)-2-methylindoline.

~'' ' ~ .;
-' ' ~ ': ~

.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of 1-phenyl-4~1auroyl-5-hydroxypyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, for example bis-(2,2,6,6-tetramethyl-piperidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert.-butyl-4-hydroxybenzylmalonic acid bis-(1,2,2,6,6-pentamethylpiperidyl)-ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenedi-amine and 4-tert.-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl)-nitrolotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate, 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

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

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-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-(benzylidene)-oxalic acid dihydrazide.

, -- . .:
:.
, ; :

:- :~ : : .
:
, ' ' . , '` ' ' - ~27~ ~ ~

4. Phosphites and phosphonites, for example triphenylphosphite, diphenyl-alkylphosphites, phenyl- dialkylphosphites, tris-(nonylphenyl)-phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.-butylphenyl)-phosphite, diisodecylpenta-erythritol diphosphite, bis-(2,4-di-tert.-butylphenyl)-pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis-(2,4-di-tert.-butylphenyl)-4,4'-biphenylene diphosphonite, 3,9-bis-(2,4-di-tert.-butyl-phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

5. Peroxide-decomposing compounds, for example esters of B-thio-di-propionic acid, for example of lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-(~-dodecylmercapto)-propionate.

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

7. Basic costabilisers, for example melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, urea derivatives, hydrazine deriva-tives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate.

8. Nucleation agents, for example 4-tert.-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcers, for example calcium carbonate, silicates, glass fibres, asbestos, talcum, kaolin, mica, barium sulfate, metal oxides and hydroxides, soot, graphite.

10. Other additives, for example plasticisers, glidants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents, propellants.

~:

.

Advantageous compositions according to the present invention are accord-ingly, for example, those which contain a~ synthetic polymers and b) at least one compound of fo}mula I, as described above. The synthetic poly-mer in the said composition is preferably a polyolefin.

Other advantageous compositions contain a) a functional fluid preferably from the group consisting of lubricants, hyclraulic fluids and metal work-ing fluids and b) at least one compound of formula I, as described above.

Lubricants are especially preferred and, of those, the mineral oils, the synthetic oils or mixtures thereof are of particular interest.

As functional fluids from the group consisting of lubricants, hydraulicfluids and metal working fluids there are used the products known per se.

The lubricants and hydraulic fluids that come into consideration are known to the person skilled in the art and are described, for example, in Dieter Klamann "Schmierstoffe und verwandte Produkte", Verlag Chemie, Weinheim, 1982, in Schewe-Kobek,"Das Schmiermittel-Taschenbuch", Dr.
Alfred Huthig-Verlag, Heidelberg, 1974, or in "Ullmanns Encyclopadie der technischen Chemie", Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

Examples thereof are lubricants and hydraulic fluids based on mineral oils, or synthetic lubricants or hydraulic fluids, especially those which are carboxylic acid ester derivatives and are used at temperatures of 200C and above.
.

Examples of synthetic lubricants include lubricants based on a diester of a divalent acid with a monovalent alcohol, for example dioctyl sebacate or dinonyl adipate, a triester of trimethylol propane with a monovalent acid or with a mixture of such acids, for example trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monovalent acid or with a mixture of such acids, for example pentaerythritol tetracaprylate, or a complex .

~i .

ester of monovalent and divalent acids with polyvalent alcohols, for example a complex ester of t}imethylolpropane with caprylic or sebacic acid or of a mixture thereof.

Especially suitable, in addition to mineral oils, are, for example, poly-~-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, and mixtures thereof with water.

The compounds of formula I are readily solu'ble in lubricants and are therefore especially suitable as additives to lubricants and attention is drawn to their surprisingly good anti-oxidative and anti-corrosive action.

The compounds of formula I are able to display their superior properties, for example, in lubricants for internal combustion engines, for example internal combustion engines according to the Otto principle. For example, in lubricating oils the compounds of formula I prevent the formation of sludge or reduce sludge formation to a surprising extent.

It is also possible to prepare so-called master batches.

The compounds of formula I are effective even in very small amounts as additives in lubricants. They are advantageously mixed with the lubri-cants in an amount of from 0.01 to 5 % by weight, preferably in an amount of from 0.05 to 3 % by weight, and especially preferably in an amount of from O.1 to 2 % by weight, in each case based on the lubricant.

The lubricants may, in addition, contain other additives which are added in order further to improve the basic properties of lubricants; these include: anti-oxidants, metal passivators, rust inhibitors, viscosity index enhancers, pour-point depressors, dispersants, detergents, high pressure additives and anti-wear additives.

For example, a number of such compounds can be found in the above list "1. Anti-oxidants"~ especially under points 1.1 to 1.10. Furthermore, other additives may be mentioned by way of example:

. I

~ . :, .2a~.

Examples oE aminic anti-oxidants: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis-(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis-(l-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-(naphth-2-yl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenadiamine, 4-(p-toluenesulfonamido)-diphenylamine, N,N'-dimethyl-N,N'-di-sec.-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydi-phenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, Eor example p,p'-di-tert.-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di-(4-methoxyphenyl)-amine, 2,6-di-tert.-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodi-phenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di-[(2-methylphenyl)-amino]-ethane, 1,2-di-(phenylamino)-propane, (o-tolyl)-biguanide, di-[4-(1',3'-dimethylbutyl)-phenyl]-amine, tert.-octylated N-phenyl-l-naphthylamine, a mixture of mono- and di-alkylated tert.-butyl-/tert.-octyl-diphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-ben 2 othiazine, phenothiazine, N-allylpheno-thiazine .

Examples of further anti-oxidants: aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithio-carbamic or dithiophosphoric acid.

Examples of metal passivators, for example for copper, are: triazoles, benzotriazoles and derivatives thereof, tolutriazoles and derivatives thereof, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2,5-dimer-captobenzotriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylene-bis-benzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidene-propylene-diamine, salicylaminoguanidine and salts thereof.

. . .
,:

: . , Examples of rust inhibitors are: a) Organic acids, their esters, metal salts and anhydrides, for example: N-oleoylsarcosine, sorbitan mono-oleate, lead naphthenate, alkenylsuccinic acid anhydride, for example dodecenylsuccinic acid anhydride, alkenylsuccinic acid partial esters and partial amides, 4-nonylphenoxyacetic acid. b) Nitrogen-containing com-pounds, for example: I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates. II. Heterocyclic corn-pounds, for example: substituted imidazolines and oxazolines. c) Phos-phorus-containing compounds, for example: amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyl dithio-phosphates. d) Sulfur-containing compounds, for example: barium dinonyl-naphthalenesulfonates, calcium petroleum sulfonates.

Examples of viscosity index enhancers are: polyacrylates, poly-methacrylatesS vinylpyrrolidone/methacrylate copolymers, polyvinyl-pyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copoly-mers, polyethers.

Examples of pour-point depressors are: polymethacrylate, alkylated naphthalene derivatives.

Examples of dispersants/su}factants/detergents are: polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of high pressure additives/anti-wear additives are: sulfur-and/or phosphorus- and/or halogen-containing compounds, such as sulfated vegetable oils, zinc dialkyl dithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl- and aryl-di- and tri-sulfides, triphenyl phosphorothionates, diethanolaminomethyltolyltriazole, di-(2-ethylhexyl)-aminomethyltolyltriazole.

The present invention also includes novel compounds of general formula Ia .

HO \ /.~ /R3 R2/ \-~ \CH2-CH-~ - - n A (Ia), wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, and R3 is -H or CH3, and n is a number from 1 to 4 or /Rs 6, and, when n is 1, A is -oR4 or -N\ , and R4 is -H, alkyl having from 5 to 45 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 2 to 18 carbon atoms, C~3/CH3 ~-\ /N- R9 C~3 CH3 or -CH2CH2-XR5a, and each of Rs and R6, independently of the other, is -H, alkyl having from 1 to 20 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, aralkyl having from 7 to 10 carbon atoms or C~3/CH3 --\ /N- R9 C~3 CH3 and, in addition, Rs may be -NH2, R9 is -H, alkyl having from 1 to 8 carbon atoms, -~-R10, -0 or -oR9', wherein R9' is -H, alkyl having from 1 to 25 carbon atoms or -~-R10, X is -0-, -S- or -N-, R is :. : . - ::
. . .:
~.. :, . . '. ::: : .,.

~CH - ~H - c-oRb -CH2-~ -OH , \R2 -H, alkyl having from l to 24 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms or -CH~-ICl-ORb, and R10 is alkyl having from 1 to 20 carbon atoms, Ra is -H or -CH3, R is -H or alkyl having from 1 to 24 carbon atoms and Rc is -H or -CH3, with the proviso that R
and R are not -CH3 at the same time, and R6a is alkyl having from l to 18 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 24 carbon atoms, or Cs-Cgcycloalkyl, or, when n is 2, A is -O-C H2 ~~~ -O-(CHzCHzO) CH2CHzO-, -O-CHz-CHz-B--CHz-CHz-O-, C~3/CH3 C~3/CH3 C~3/CH3 -0--\ /N-(CHz)z-O- , -0--\ /N-CHzCH=CH-CH2-N\ /--0- , C~3 CH3 C~3 CH3 C~3 CH3 C~3/CH3 C\3~CH3 -0--~ /N-(CHz)bl-N\ /--0- , C~3 CH3 CH3 CH3 -O-CHzCH=CHCH2-O-, -O-CHzC-CCH2-O-, -O-CHzCH2NH-~-~-NH-CHzCH2-O-, ,CH3 ,_.
-O~CH2-CH2-O--~ / -¢ \ ~--O-CHz-CH2-O-.

-0--~ 0- , / I \- or - ~(CHz) wherein a is a number from 1 to 30, x is a number from 2 to :. ~ . , .~ ., . , :

.

2~ 4.11.

~12 ' R or S ~13S- , RA is alkyl having from 1 to 20 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 20 carbon atoms, cyclohexyl or CH3\ /CH3 --\ /N-R9 CH; CH3 and each of R11, R1 2 and R13, independently of the others, is -H, alkyl having from 1 to 12 carbon atoms or phenyl, or Rl2 and R13 together with the carbon atom to which they are bonded form a cycloalkyl ring having from 5 to 12 carbon atoms, b1 is a number from 2 to 10 and b2 is a number ÇHzCHzo_ from 0 to 6, or, when n is 3, A is -OCH2CHz-~-CH2CHzO- or -0-CHz- H-CHz-0-, or, when n is 4, A is !/_\. or i/_~ i or, when n is 6, A is ICHz-O-0 - - CHz-~-CH20-Advantageous compounds of formula Ia are those wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, and R3 is -H, and n is a number from 1 to 4 or 6, wherein, when n is 1, A is -oR4 /Rs or -N~ , and R4 is -H, alkyl having from 5 to 20 carbon atoms, " ~:

.: ~ , :. : .

2~

cyclohexyl, alkenyl having from 2 to 18 carbon atoms or -CH2CH2-XR5 , and Rs is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl, Cl-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, benzyl or -NH2, anbd Rs is -H or alkyl having from 1 to 12 carbon atoms, X is -O-, -S- or -~- , R is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl or ~Rl -CHz~ --OH
\R2 and R a is alkyl having from 1 to 12 carbon atoms, phenyl, or phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH20)aCH2CH20-, -O-CHz-CH2-B-CH2-CH2-O-.
H3C~ ~CH3 H3C~ ~CH3 -O--~ ~N-(CH2?bl-N~ ~--O--O-CH2CH=CHCH2-O-, -O-CH2CH2NH-~-~-NH-CH2CH2-O-, C,H3 ._.
-O-CH2-CH2-O--~ ~-~ o-cH2-cH2-o- .

_ ~3 _ \ ~.~ / ~ - ~(CH~) wherein a is a number from 1 to 12, x is a number from 2 to 12, B is -S-or -~-, RA is alkyl having from 1 to 12 carbon atoms, phenyl, phenyl , . .
,. . ..
- . .

,,:. :' substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms or cyclohexyl, and R11 is -H, alkyl having from 1 to 12 carbon atoms or phenyl, and b1 is a number from 2 to 6 and _ 2 is a ÇHzCHzo_ number from O to o, or, when n is 3, A is -OCHzCH2-~-CH2CH20-or -O-CH2-CH-CH2-O-, or, when n is 4, A is -O- -O i/ _\ or ~

or, when _ is 6, A is CIHz--O--O - - CHz-~-CHzO-CHz-O- 2 Especially advantageous compounds of formula Ia are those wherein R1 isalkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, R2 is -H, alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, and R3 is Rs -H, and n is 1 and A is -oR4 or -~\ , wherein R4 is -H, alkyl having from 5 to 18 carbon atoms, cyclohexyl, -CHzCH=CH2, -(CH2)7-CH=CH-(CH2)7CH3, H3C\ /CH3 ._.

or -CHzCH2XR , wherein R9 is -H, alkyl having from 1 to 4 carbon atoms, -O , -O-alkyl having from 1 to 4 carbon atoms or cyclohexyl, X is -O-, 6a -S- or -~- , R6a is -H, alkyl having from 1 to 18 carbon atoms, phenyl, -CH2-C-OR , . .

H C~H ~_oRb \ _ wherein R is alkyl having from 1 to 24 carbon atoms, R is -H or -CH3, R is -H and R is alkyl having from 1 to 12 carbon atoms or phenyl, and each of Rs and R6, independently of the other, is -H, alkyl having from 1 to 12 carbon atoms, phenyl, or H3C\ /CH3 --\ /N-R9 wherein R9 is as defined above, or Rs is -NH2 and Rs is -H, or _ is 2, in which case A is -O-CxH2 -O- and x is 2 to 8.
x Preferred are compounds of formula Ia wherein R1 is tert.-butyl, R2 is : -H, methyl or tert.-butyl, and R3 is -H, and n is 1, in which case A is s -oR4 or -N\ , and R4 is alkyl having from 6 to 18 car'von atoms, -(CH2)7-CH=CH-(CH2)7CH3, H3C\ /CH3 --\ /N-(H,CH3) or -CH2CHz-SR wherein R is -H or -CH2-CH2-~-O-R , wherein R is n-C4Hg to n-CgH1 7 or tert.-CI,H9 to tert.-CaH1 7, or n is 2, in which case A is -O-CxH2 -O- and x is 2 to 8, or A is -O-(CH2-CH2-O-)a-CH2-CH2-O- and a is 1 to 4, or A is -O-CH2-CHz-b-CH2-CH2-O- and B is -S-, -~- or A
-S- , wherein RA is C4-C8alkyl or phenyl, R1 2 is H or C1-Cgalkyl and . Rl3 is H, C1-Cgalkyl or phenyl, or A is i.

.
: :
', ', , ' , '': ~ , H3C\ /CH3 H3C\ /CH3 H3C\ /CH3 -o-.\ /N-(CHz)2-O- , ---\ /N-CH2CH=CH-CH2-N\ /.-o- or H3C\ /CH3 H3C\ /CH3 --O--\ /N-(CH2)b1- ~ / ~

wherein _1 is 2 to 6, or A is -O-CI12-CH=CH-CH2-O-, -O-CH2-C-C~CH2-O-, / ¦ \- , -O-CHz-CH2-NH-ICl-~-NH-CH2-CH2-O- or -~-(CH2)b2 ~
.

wherein b2 is O to 6 and R11 is -H or C1-C8alkyl.

Further preferred compounds of formula Ia are those wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl and R3 is -H and n is l and A is -oR4 and R4 is C~-Clgalkyl.

Other compounds of formula Ia include those wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl and R3 is -H, and n is 2 and A is -O-C H2 ~~
and x is 2 to 6, or A is -O-(CH2-CH2-O) -CH2-CH2-O-and a is l, 2 or 3, or A is -O-CH2-CH2-B-CH2-CH2-O- and B is -S- or ~
,~ \.

or A is -O-CH2-CH2-NH-ICl-lCl-NH-CH2-CH2-O- or A is -NH-NH-.

i : , , ~ .

..

Also preferred are compounds of formula Ia wherein R~ is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, R3 is -H, n is l and A is -oR4, wherein R4 is C6-C13alkyl, or n is 2 and A is -O-CxH2x-O and x is 2 to 6~
-OCHzCH2-S-CH2CHzO- or -O(CH2CH20) CH2CH2-O- and a is 1 to 4.

Compounds of formula Ia of the above-mentioned type wherein a is 1 or 2are especially preferred.

Also preferred are compounds of formula Ia oE the above-mentioned type wherein R4 is alkyl having from 9 to 18 carbon atoms.

Also preferred are compounds of formula Ia wherein R1 is tert.~butyl, R2 is -H, -CH3, tert.-butyl and R3 is -H and n is 3 and A is C,HzCH2-O--O-CH2CH2-~-CHzCHz-O-~ or n is 4 and A is _o_.
-O-o-or n is 6 and A is O - - CHz-~-CH20-CHz-O- 2 Particularly preferred are compounds from the series having the formulae IC(CH3)3 \.~ \.
(H3C)3C ~/ \CH2CH-C-O-CH2-CH2 - 2 Cl(CH3)3 HO\ ~-(H3C)3C ~- CHzCH-ICl-O-CH2-CH2 - - O

: .

- '~o -Cl(CH3)3 }10~

(H3C)3C ~- CH2~H-~-oR4 wherein R4 C8-C18alkyl and especially -isoC3H17, -n-C12H7s or -n-C1gH37, C(CH3)3 CltCH3)3 HO\ ~ -\ /OH
! i! ~H3 H3 ! i!
(H3C)3C ~- CH2-CH-~-O-(CH2)~-O-lCI- H- C~z~- C(CH3)3 and I IC(CH3)3 HO\ ~- , ~(N~C)IC ~ CHz- H-C-C CH -CHz N~

The scope of the present invention also includes the use of compounds of formula I in accordance with the above description as anti-oxidants in organic materials that are sensitive to oxidative, thermal or actinic degradation. The materials ~ se and also their preferred groups and compounds are defined above.

The use of the compounds of formulae I and Ia in lubricants is especially preferred.

The following Examples further illustrate the present invention but do not limit the scope thereof. Unless indicated to the contrary, parts and percentages always relate to weight.

~: . , - : - - . ,:

Example 1: Octadecyl-2-methYl-3-(3',5'-di-tert.-butYl-4'-hYdroxYPhenyl)propionate OIH IOH
(H3C)3C\ ~-\ /C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 + HO-n-ClgH37 ) ! 1! + CH30H
~-/ O ~-/
CHz-ÇH-C~ CHz-ÇH-C
CH OCH3 CH3 O-n-C1gH3 7 30.6 g (0.1 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-'nydroxy-phenyl)-propionate and 27 g (0.1 mol) of 1-n-octadecanol are placed in a 4-necked glass flask and heated to 100C. Then 0.25 g (1 mol ~/O) oE
dibutyltin oxide is added and the mixture is heated to 180C, with methanol being split off. The temperature is maintained at 180C for 6 hours.

The reaction mixture is neutralised with HCl (20 %) and dried under a high vacuum.

52.4 g - 96.2 % of the theoretical yield of a slightly yellowish oil are obtained, the oil crystallising slowly. The melting point is then above 40C.
nalysis: calculated 79.35 % C 11.84 % H
found 79.57 % C 11.68 % H

Example 2: n-Nonyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxYphenyl)-propionate IOH IOH
(H3C)3C\ ~-\ /C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 I ll + HO-CgHlg-n , i il ~- R C ~- R
./ \O/ 3 \./ \O-nCgHl9 , , , : ~

.

30.6 g of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate and 14.4 g of n-nonyl alcohol are placed in a 100 ml sulfonat-ing flask and heated to 100C. 0.2 g of dibutyltin oxide is added and the temperature is increased to 150C. Methyl alcohol is split off from a temperature of 125C. The reaction is maintained at 150C for 6 hours.

The batch is dissolved in 60 ml of toluene, concentrated in a rotary evaporato} and dried for 2 hours at 80C under a high vacuum.

39.4 g a 94 ~0 of the theoretical yield of a slightly yellowish viscous oil are obtained.
nalysis: calculated 77.46 % C 11.08 % H
found 77.35 % C 10.93 % H
he reaction is repeated analogously to Example 2; according to:

Example 3: By reaction of isononyl alcohol, after a reaction period of 7 hours at 140C, a yellowish oil containing 96.8 % isononyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate is obtained.

Analysis: calculated 77.46 % C 11.08 % H
found 77.33 % C 11 % H
-Example 4: Diethylene glYcol bis-[2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate]
IOH
(H3C)3C\ ~-\ /C(CH3)3 /C~2 /C~H2 2 1 Ij + HO \ /O \ OH
~ / CH2 CH/2 H2l-~- C-O-CH3 ~ ' ' ,, ', '' ~' .

:

2~

OIH IOH
(H3C)3C\ ~-\ /C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 I i1 1 + 2CH30H
/ HzC - 0 - Ch2 ~-/

61.2 g (0.2 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxy-phenyl)-propionate and 10.6 g (0.1 mol) of diethylene glycol are placed in a 4-necked glass flask and heated to 100C. Then 0.5 g - 1 mol % of dibutyltin oxide is added and the reaction mixture is heated to 180C, with methanol being split off. The temperature is maintained for 5 hours.
Working up is effected by drying under a high vacuum.

64.2 g - 98 % of the theoretical yield of a brown viscous oil are obtained. This oil is then purified by column chromatography, a slightly yellowish viscous oil being obtained in a yield of 79.4 % of the amount used.
nalysis: calcula~ed 73.26 % C 9.54 % H
found 73.51 % C 9.38 % H

Example 5: Thiodiethylene glycol bis-[2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate]
OIH
(H3C)3C\ ~-\ /C(CH3)3 2 ! I! /C~HZ /C~H2 ~ / + H0 \ S \ OH -R c~2 C~2 HzC- ~- C- O-CH3 IOH OIH
(H3C)3C\ ~\ /C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 !~ ,i! !~ ,il ~ 2 CH30H
H 2 c--~--8--o ~ j ,s ~ o--c--~--CHz H3 CHzC~2 H3 .

91.9 g (0.3 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxy-phenyl)-propionate and 18.3 g (0.15 mol) of thiodiethylene glycol are placed in a 4-necked glass flask and heated to 100C. 0.4 g of dibutyltin oxide - 0.5 mol % is added and the mixture is heated to 180C, with methanol being split off. The temperature is maintained at lôOC for 6 hours.

After washing with water and drying under a high vacuum, 96.3 g - 95.7 % of the theoretical yield of a brown oil are obtained.

The brown oil is then purified by column chromatography, a yield of 72.4 % of the amount used being obtained in the form of a light-brown viscous oil.
nalysis: calculated 71.60 % C 9.31 % H 4.78 % S
found 71.66 % C 9.08 % H 4.90 % S

Example 6: Dodecyl-2-methyl-3-(3',5'-di-tert.-buty1-4'-hYdroxyphenyl)-propionate IOH ~H
(H3C)3C\ ~-\ /C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 i il + HOCl2H2s )I i1 ~, /- ~ /-H2l-~-C-O-CH3 H2l-~-C-O-C12H2s 30.6 g (0.1 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxy-phenyl)-propionate and 18.6 g (0.1 mol) of 1-dodecanol are placed in a 4-necked glass flask and heated to 100C, then 0.25 g - 1 mol % of dibutyltin oxide is added and the mixture is heated further to 180C, with methanol being split off. The reaction mixture is maintained at 180C for 6 hours.

The mixture is then dried under a high vacuum. 45.8 g - 99.3 % of the theoretical yield of a slightly yellowish oil are obtained.

i !
, ~' ~' ' . , .

:

nalysis: calculated 78.20 % C 11.38 % H
found 78.32 % C 11.27 % H

Example 7: 2-~thylhexYl-[2-methyl-3-(3',5'-di-te~t.-butyl-4'-hydroxy-phenyl)-propionate]
~H
(H3C)3C\ ~-\ /C(CH3)3 ~C~2~C~2~C~2 ! i! + H0 C,h Ch2 CH3 - ~
~ / H2C-CH3 H2C-~-~-0-CH3 IOH
(H3C)3C\ ~-\ /C(CH3) 3 i!

H C-~ cR-o/ ~C~ ~Ch/ ~CH

61.3 g (0.2 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxy-phenyl)-propionate and 26 g (0.2 mol) of 2-ethyl-1-hexanol are placed in a 4-necked glass flask and heated to 100C. Then 1 g (2 mol %) of dibutyltin oxide is added and the temperature is increased to 180C, with methanol being split off. The reaction mixture is maintained at 180C for 9 hours. The end product is obtained in pure form, without working up, as a slightly yellowish resin in a yield of 79.4 g - 98.2 % of the theoretical yield.
nalysis: calculated 77.18 % C 10.96 % H
found 77.05 % C 11.03 % H

~xample 8: 1,6-Hexanediol bis-[2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate]
OIH
(H3C)3C\ ~-\ /C(CH3)3 2 ¦ i1 1 HO~CH2~60H
~ /
H2C-~-C-0-CH3 .

;

4~.

OIH
IOH (H3C)3C C(CH3)3 (H3C)3C\ ~-\ /C(CH3)3 \
.
8 ,C~2,c~2,c~2 o--c--~ CH2 H2C-~- -0 Ch2 Ch2 C~2 H3 46 g (0.15 mol) of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxy-phenyl)-propionate and 8.9 g (0.075 mol) of 1,6-hexanediol are placed in a 200 ml 4-necked glass flask and heated to 100C. Then 0.38 g a 2 mol % of dibutyltin oxide is added and the reaction mixture is then heated to 180C, with methanol being split off. The reaction i~s maintained at 180C for 6 hours. The subsequent working up is effected by crystallisation of the batch from 100 ml of a mixture of isopropanol and water (7:3), filtration with suction and washing with 2 x 30 ml of a cold isopropanol/water mixture (7:3) and drying in an oven at 50C.

The yield is 24.7 g a 49.4 % of the theoretical yield of a light-beige pulverulent product.

Analysis: calculated 75.63 % C 9.97 % H
found 75.85 % C 9.97 % H

Example 9:

(H3C)3C\ ~-\ /C(CH3)3 (H3C)3C\ ~ /C(CH3)3 N(CH2CH20H)3 + 3 1 il ~~ il .~ ..~ . /N ~ 3 CH30H
C~ 0-CH3 /~2 ~\ /C~2 ~ ~

4.5 g of N-triethanolamine and 30.6 g of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate are placed in a 100 ml sulfonat-ing flask having a descending "Liebig'l condenser under a gentle current of nitrogen. The mixture is heated to 120C and 0.25 g of dibutyltin oxide is added, and then the temperature is increased to 160C, with MeOH
being split off. The reaction temperature is maintained at 160C for 6 hours.

The batch is cooled to 80C, then taken up in 60 ml of toluene and con-centrated in a rotary evaporator. 26.o g of a light-brown oil are obtained.

After purification by "flash" chromatography using toluene:ethy].
acetate = 9:1 as solvent, 23.6 g - 81.1 % of the theoretical yield of a light-brown oil are obtained.
Analysis: foundcalculated 74.32 74.11 % C
9.65 9.64 % ~1 1.52 1.44 % N

Example 10:
OIH OIH
(H3C)3C\ ~-\ /C(CH3)3(H3C)3C\ ~-\ /C(CH3)3 + NH2-NH2-H20 ~ I i1 C~ ~C\ /CH3 ~ ~ H-NH2 46 g of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-pro-pionate are placed in 100 ml of ethanol and, at room temperature, added dropwise within a period of 30 minutes to a clear slightly yellowish solution of 7.5 g of hydrazine hydrate. The temperature is increased, the ethanol is distilled off and then the reaction temperature is increased to 100C, a thick unstirrable paste being obtained. After cooling to room temperature and mixing with hexane, the mixture is filtered with suction and dried in an oven at 60.

. . , : , .
,~ ~

2~

39.8 g -^ 86.5 % of the theoretical yield of a white powder having a melting point of 128C are obtained.
Analysis: found calculated 70.72 70.55 % C
10.03 9.87 % H
9.03 9.14 % N

Example 11:

~ CH2CHzOH (H3C)3C\ ! /C(CH3)3 \ /-- ~ + 2 1 i1 =- CH2CH20H

C~2 ~
~CH3 - lOH
( 3 )3 ~ C(cH3)3 N- -CH2CHzO~\ ~CHz ~ 2CH30H

18.1 g of N-phenyldiethanolamine and 61.3 g of methyl-2-methyl-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate are placed in a 350 ml sul-fonating flask ha~ing a descending "Liebig" condenser under a gentle current of nitrogen. The reaction mixture is heated to 120C, 0.5 g of dibutyltin oxide is added and the temperature is increased to 160C, with ~eOH being split off. The mixture is left for 8 hours at 150C to com-plete the reaction. The batch is cooled to 80C and taken up in 100 ml of toluene, then concentrated in a rotary evaporator, yielding 74 g of a brown oil.

Purification is effected by means of "flash" chromatography using toluene:ethyl acetate 9:1 as solvent.

; "
, .

, :- , . . , : :
. .

59.5 g - 81.5 % of the theoretical yield of an orange oil are obtained.
Analysis:found calculated 75.68 75.83 % C
9.25 9.26 % H
1.92 1.87 % N

Example 12: Some of the compounds according to Examples 1 to 11 are tested for their suitability as stabilisers against the oxidative degradation of a lubricating oil.

A commercially available mineral lubricating oil (Mobil 15 SS 4) is mixed with 0.05 % by weight of a commercially available corrosion inhibitor of the alkenylsuccinic acid semiester type.

The individual stabilisers, corresponding to the preceding Examples, are then added to the prepared oil in an amount of 0.25 % by weight, based on the oil, and the resulting stabilised oils are subjected to an oxidation test.

The test method is known as the TOST test (oxidation characteristics of mineral oil Mobil 15 SS 4, ASTM D 934/DIN 51587/IP 157).

The oil to be tested is heated at 95C in the presence of water, oxygen, an iron/copper catalyst and the stabiliser for 500 hours. Then the acid value TAN (in mg of KOH consumption per g of test oil) and the sludge (in mg of residue per batch) are determined. The results are given in Table 1.

- : : . - , .' , ~ :`
- , ..
, ~: .
..

'c~, Stabiliser 500 hours TOST
according to TAN (mg KOH/g oil) SLUDGE (mg) _ Example 1 0.11 22 _ Example 2 0.20 103 _ Example 3 0.30 76 Example 4 0.06 30 Example 7 0.09 72 Example 8 0.07 33 without >2.0 >1000 ~ . ,. ~, . .
,. ; . : , .

. . , , .
~ ' ` : i '

Claims

1. A composition containing a) at least one organic material subject to oxidative, thermal or actinic degradation and b) at least one compound of general formula I

(I), wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, and R3 is -H or CH3, and n is a number from 1 to 4 or 6, and, when n is 1, A is -OR4 or , and R4 is -H, alkyl having from 1 to 45 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 2 to 18 carbon atoms, or -CH2CH2-XR5a, and each of R5 and R6, independently of the other, is -H, alkyl having from 1 to 20 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8carbon atoms, aralkyl having from 7 to 10 carbon atoms or and, in addition, R5 is -NHz, R9 is -H, alkyl having from 1 to 8 carbon atoms, , -O? or -OR9', wherein R9' is -H, alkyl having from 1 to 25 carbon atoms or , X is -0-, -S- or , R5a is , , -H, alkyl having from 1 to 24 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms or , and R10 is alkyl having from 1 to 20 carbon atoms, Ra is -H or -CH3, Rb is -H or alkyl having from 1 to 24 carbon atoms and Rc is -H or -CH3, with the proviso that Ra and Rc are not -CH3 at the same time, and R6a is alkyl having from 1 to 18 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 24 carbon atoms, or C5-C8cycloalkyl, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH2O)aCH2CH2O-, -O-CH2-CH2-B-CH2-CH2-O-, , , , -O-CH2CH=CHCH2-O-, -O-CH2C=CCH2-O-, , , , or wherein a is a number from 1 to 30, x is a number from 2 to 20, B is -S- , or , RA is alkyl having from 1 to 20 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 20 carbon atoms, cyclohexyl or and each of Rll, Rl2 and Rl3, independently of the others, is -H, alkyl having from 1 to 12 carbon atoms or phenyl, or R12 and R13 together with the carbon atom to which they are bonded form a cycloalkyl ring having from 5 to 12 carbon atoms, b1 is a number from 2 to 10 and b2 is a number from 0 to 6, or, when n is 3, A is or , or, when n is 4, A is or or, when n is 6, A is .

2. A composition according to claim 1, containing at least one compound of formula I wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, and R3 is -H, and _ is a number from 1 to 4 or 6, wherein, when n is 1, A is -OR4 or , and R4 is -H, alkyl having from 1 to 20 carbon atoms, cyclohexyl, alkenyl having from 2 to 18 carbon atoms or -CH2CH2-XR5a, and R5 is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, benzyl or -NH2, and R6 is -H or alkyl having from 1 to 12 carbon atoms, X is -O-, -S- or , R5a is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl or and R6a is alkyl having from 1 to 12 carbon atoms, phenyl, or phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH2O)aCH2CH2O-, -O-CH2-CH2-B-CH2-CH2O-, -O-CH2CH=CHCH2-O-, , , , or wherein a is a number from 1 to 12, x is a number from 2 to 12, B is -S-or , RA is alkyl having from 1 to 12 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms or cyclohexyl, and R11 is -H, alkyl having from l to 12 carbon atoms or phenyl, and b1 is a number from 2 to 6 and b2 is a number from O to 6, or, when n is 3, A is or , or, when n is 4, A is or or, when n is 6, A is .

3. A composition according to claim 1, containing at least one compound of formula I wherein R1 is alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, R2 is -H, alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, and R3 is -H, and n is 1 and A is -OR4 or , wherein R4 is -H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, -CH2CH=CH2, -(CH2)7-CH=CH-(CH2)7CH3, or , wherein R9 is -H, alkyl having from 1 to 4 carbon atoms, -O?, -O-alkyl having from 1 to 4 carbon atoms or cyclohexyl, X is -O-, -S- or , R5a is -H, alkyl having from 1 to 18 carbon atoms, phenyl, , or wherein Rb is alkyl having from 1 to 24 carbon atoms, Ra is -H or -CH3, Rc is -H and R6a is alkyl having from 1 to 12 carbon atoms or phenyl, and each of R5 and R6, independently of the other, is -H, alkyl having from 1 to 12 carbon atoms, phenyl or wherein R9 is as defined above, or R5 is -NH2 and R6 is -H, or n is 2, in which case A is -O-CxH2x-O- and x is 2 to 8.

4. A composition according to claim 1, containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, methyl or tert.-butyl, and R3 is -H, and n is 1, in which case A is -OR4 or , and R4 is alkyl having from 1 to 18 carbon atoms, (CH2)7-CH=CH-(CH2)7CH3, or -CH2CH2-SR5a wherein R5a is -H or , wherein Rb is n-C4H9 to n-C8H17 or tert.-C4H9 to tert.-C8H17, or n is 2, in which case A is -O-CxH2x-O- and x is 2 to 8, or A is -O-(CH2-CH2-O-)a-CH2-CH2-O- and a is 1 to 4, or A is -O-CH2-CH2-B-CH2-CH2-O- and B is -S-, or , wherein RA is C4-C8alkyl or phenyl, R12 is H or C1-C8alkyl and R13 is H, C1-C8alkyl or phenyl, or A is , or wherein b1 is 2 to 6, or A is -O-CH2-CH=CH-CH2-O-, -O-CH2-C=C-CH2-O-, , or wherein b2 is 0 to 6 and R11 is -H or C1-C8alkyl.

5. A composition according to claim 1, containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, and R3 is -H and n is 1 and A is -OR4 and R4 is C1-C10alkyl.

6. A composition according to claim 1, containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, and R3 is -H, and n is 2 and A is -O-CxH2-O- and x is 2 to 6, or A is -O-(CH2-CH2-O)a -CH2-CH2-O- and a is 1, 2 or 3, or A is -O-CH2-CH2-B-CH2-CH2-O- and B is -S- or , or A is or A is -NH-NH-.

7. A composition according to claim 1, containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, R3 is -H, n is 1 and A is -OR4, wherein R4 is C1-C18alkyl, or n is 2 and A
is -O-CxH2x-O-, and x is 2 to 6, -OCH2CH2-S-CH2CH20- or -O(CH2CH2O)aCH2CH2-O-and a is 1 to 4.

8. A composition according to claim 7, containing at least one compound of formula I wherein a is 1 or 2.

9. A composition according to claim 1, containing at least one compound of formula I wherein R1 is tert.-butyl, R2 is -H, -CH3, tert.-butyl, and R3 is -H, and n is 3 and A is , or n is 4 and A is or n is 6 and A is

10. A composition according to claim 1, containing at least one compound from the series of formulae , , , wherein R4 is C1-C18alkyl, and ,

11. A composition according to claim 1, containing a) a functional fluid from the group consisting of lubricants, hydraulic fluids and metal work-ing fluids or a synthetic polymer and b) at least one compound of formula I according to claim 1.

12. A composition according to claim 1 containing a) a lubricant from the group consisting of mineral oils, synthetic oils or a mixture thereof and b) at least one compound of formula I according to claim 1.

13. A composition according to claim 1, containing at least one compound according to claim 10.

14. A composition according to claim 1, containing a) a synthetic polymer and b) at least one compound of formula I according to claim 1.

15. A composition according to claim 14, containing a) a polyolefine and b) at least one compound of formula I according to claim 1.

16. A compound of general formula Ia (Ia), wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or aralkyl having from 7 to 9 carbon atoms, and R3 is -H or CH3, and n is a number from 1 to 4 or 6, and, when n is 1, A is -OR4 or , and R4 is -H, alkyl having from 5 to 45 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 2 to 18 carbon atoms, or -CH2CH2-XR5a, and each of R5 and R6, independently of the other, is -H, alkyl having from 1 to 20 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, aralkyl having from 7 to 10 carbon atoms or or R5 is -NH2, R9 is -H, alkyl having from 1 to 8 carbon atoms, .
-O? or -OR9', wherein R9' is -H, alkyl having from 1 to 25 carbon atoms or , X is -O-, -S- or , R5a is , , -H, alkyl having from 1 to 24 carbon atoms, phenyl, cycloalkyl having from 5 to 12 carbon atoms or , and R10 is alkyl having from 1 to 20 carbon atoms, Ra is -H or -CH3, Rb is -H or alkyl having from 1 to 24 carbon atoms and Rc is -H or -CH3, with the proviso that Ra and Rc are not -CH3 at the same time, and R6a is alkyl having from 1 to 18 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 24 carbon atoms, or C5-C8cycloalkyl, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH2O)aCH2CH2O-, -O-CH2-CH2-B-CH2-CH2-O-, , , , -O-CH2CH=CHCH2-O-, -O-CH2C=CCH2-O-. , , or wherein a is a number from 1 to 30, x is a number from 2 to 20, B is -S- , or , RA is alkyl having from 1 to 20 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 20 carbon atoms, cyclohexyl or and each of R11, R12 and R13, independently of the others, is -H, alkyl having from 1 to 12 carbon atoms or phenyl, or R12 and R13 together with the carbon atom to which they are bonded form a cycloalkyl ring having from 5 to 12 carbon atoms, b1 is a number from 2 to 10 and b2 is a number from 0 to 6, or, when n is 3, A is or , or, when n is 4, A is or or, when n is 6, A is .

17. A compound of formula Ia according to claim 16, wherein R1 is alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, R2 is -H, alkyl having from 1 to 18 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, phenyl or benzyl, and R3 is -H, and n is a number from 1 to 4 or 6, wherein, when n is 1, A
is -OR4 or , and R4 is -H, alkyl having from 5 to 20 carbon atoms, cyclohexyl, alkenyl having from 2 to 18 carbon atoms or -CH2CH2-XR5a, and R5 is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl, C1-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkenyl having from 3 to 8 carbon atoms, benzyl or -NH2, and R6 is -H or alkyl having from 1 to 12 carbon atoms, X is -O-, -S- or , R5a is -H, alkyl having from 1 to 12 carbon atoms, phenyl, cyclohexyl or , and R6a is alkyl having from 1 to 12 carbon atoms, phenyl, or phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms, or, when n is 2, A is -O-CxH2x-O-, -O-(CH2CH2O)aCH2CH2O-, -O-CH2-CH2-B-CH2-CH2-O-, -O-CH2CH=CHCH2-O-. , , , or wherein a is a number from 1 to 12, x is a number from 2 to 12, B is -S-or , RA is alkyl having from 1 to 12 carbon atoms, phenyl, phenyl substituted by one or more alkyl groups having a total of from 1 to 18 carbon atoms or cyclohexyl, and R11 is -H, alkyl having from 1 to 12 carbon atoms or phenyl, and b1 is a number from 2 to 6 and b2 is a number from 0 to 6, or, when n is 3, A is or , or, when n is 4, A is or or, when n is 6, A is .

18. A compound of formula Ia according to claim 16 wherein R1 is alkyl having from 1 to 8 carbon atoms, cyclohexyl or phenyl, R2 is -H, alkyl having from l to 8 carbon atoms, cyclohexyl or phenyl, and R3 is -H, and n is l and A is -OR4 or, wherein R4 is -H, alkyl having from 5 to 18 carbon atoms, cyclohexyl, -CH2CH=CH2, -(CH2)7-CH=CH-(CH2)7CH3, or -CH2CH2XR5a, wherein R9 is -H, alkyl having from 1 to 4 carbon atoms, -O?, -O-alkyl having from 1 to 4 carbon atoms or cyclohexyl, X is -O-, -S- or , R5a is -H, alkyl having from 1 to 18 carbon atoms, phenyl, , or wherein Rb is alkyl having from 1 to 24 carbon atoms, Ra is -H or -CH3, Rc is -H and R6a is alkyl having from 1 to 12 carbon atoms or phenyl, and each of Rs and R6, independently of the other, is -H, alkyl having from 1 to 12 carbon atoms, phenyl, or wherein R9 is as defined above, or R5 is -NH2 and R6 is -H, or n is 2, in which case A is -O-CXH2x-O- and x is 2 to 8.

19. A compound of formula Ia according to claim 16, wherein R1 is tert.-butyl, R2 is -H, methyl or tert.-butyl, and R3 is -H, and n is 1, in which case A is -OR4 or , and R4 is alkyl having from 6 to 18 carbon atoms, -(CH2)7-CH=CH-(CH2)7CH3, or -CH2CH2-SR5a wherein R5a is -H or , wherein Rb is n-C4H9 to n C8H17 or tert.-C4H9 to tert.-C8H17, or n is 2, in which case A is -O-CxH2x-O- and x is 2 to 8, or A is -O-(CH2-CH2-O-) -CH2-CH2-O- and a is 1 to 4, or A is -O-CH2-CH2-B-CH2-CH2-O- and B is -S- , or , wherein RA is C4-C8alkyl or phenyl, R12 is H or C1-C8alkyl and R13 is H, C1-C8alkyl or phenyl, or A is , or wherein b1 is 2 to 6, or A is -O-CH2-CH=CH-CH2-O-, -O-CH2-C=C-CH2-O-, , or wherein b2 is 0 to 6 and R11 is -H or C1-C8alkyl.

20. A compound of formula Ia according to claim 16, wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl and R3 is -H and n is 1 and A is -OR4 and R4 is C6-C18alkyl.

21. A compound of formula Ia according to claim 16, wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl and R3 is -H, and n is 2 and A
is -0-CxH2x-O- and x is 2 to 6, or A is -O-(CH2-CH2-O)a-CH2-CH2-O- and a is 1, 2 or 3, or A is -O-CH2-CH2-B-CH2-CH2-O- and B is -S- or , or A is or A is -NH-NH-.

22. A compound of formula Ia according to claim 16, wherein R1 is tert.-butyl, R2 is -H, -CH3 or tert.-butyl, R3 is -H, n is 1 and A is -OR4, wherein R4 is C6-C18alkyl, or n is 2 and A is -O-CxH2x-O- and x is 2 to 6, -OCH2CH2-S-CH2CH2O- or -O(CH2CH2O) CH2CH2-O- and a is 1 to 4.

23. A compound of formula Ia according to claim 22, wherein a is 1 or 2.

24. A compound of formula Ia according to claim 16 wherein R1 is tert.-butyl, R2 is -H, -CH3, tert.-butyl and R3 is -H and n is 3 and A is , or n is 4 and A is .

or n is 6 and A is .

25. A compound of the formula Ia according to claim 16, wherein R4 is alkyl having from 9 to 18 carbon atoms.

26. A compound according to claim 16 from the series having ths formulae , , , wherein R4 is C8-C18alkyl, and .

27. Process of improving the anti-oxidant properties of organic materials that are sensitive to oxidative, thermal or actinic degradation by in-corporation of at least one compound of formula I according to claim 1 into said organic materials.

28. Process of improving the anti-oxidant properties of lubricants by incorporation of at least one compound of formula I according to claim 1 into said lubricant.

FO 7.3/HB/cp*/bg*