DD297443A5 - LUBRICANT COMPOSITIONS - Google Patents

Abstract

Lubricants can be stabilized against oxidation by addition of a) a sterically hindered amine and b) a phenol of the formula I in which A, B and X have the meanings given in claim 1. Preference is given to using phenols of the formula I which contain a thioether group. Formula I {lubricant composition; Stabilization against oxidation; sterically hindered amine; Phenol; Phenol with thioether group}

Description

The present invention relates to lubricant compositions stabilized against oxidative degradation. The stabilization takes place by adding at least two specific additives.

It is known and customary to add to lubricants based on mineral oils or synthetic oils additives to improve their performance properties. Of particular importance are additives against oxidative degradation of the lubricants, so-called antioxidants. The oxidative degradation of lubricants plays a major role, especially in engine oils, since there are high temperatures in the combustion chamber of the engine and, in addition to oxygen, nitrogen oxides (NO _x ) are present, which act as oxidation catalysts.

As antioxidants for lubricants, especially organic sulfur and phosphorus compounds are used, but also aromatic amines and phenols, in particular sterically hindered phenols (see, for example, Ulimanns Encyklopadie der technischen Chemie, 4th Edition, Verlag Chemie, Volume 20 [1981]; 541-53).

Hindered amines have also been proposed as stabilizers for lubricating oils, e.g. In US-A-4 069199 or JP-A-85/28496.

EP-A-356677 has proposed mixtures of aromatic amines and sterically hindered amines as antioxidants for lubricants, phenolic antioxidants also being able to be added to these mixtures.

It has been found that combinations of phenolic antioxidants with sterically hindered amines, even without the addition of aromatic amines, are outstandingly suitable for stabilizing lubricants.

The present invention relates to a lubricant composition containing

(A) a mineral or synthetic oil or a mixture of such oils,

(B) at least one sterically hindered amine and

(C) at least one phenol of the formula I,

wherein A is hydrogen, C, -C ₂₄ alkyl, Ce-C ^ cycloalkyl, Cr-C ₉ phenylalkyl, phenyl or a group -CH ₂ -SR ¹ or

-CH ₂ - ^N jB

BC) -C ₂₄ alkyl, Cs-C ^ cycloalkyl, _C7-C9 phenylalkyl, phenyl or a group -CH ₂ -SR ^1, X is hydrogen, C, -C, _e alkyl, or one of the groups - C, H ₂ , -S _q -R ² , -C ₆ H ₂₀ -CO-OR ³ , -C _b H ₂ b-CO-N (R ⁶ ) (R ^e ), -CH ₂ N (R ¹⁰ J (R ") or

• - ·

-CH ₂ - ^ ^ - 0H means

R ^{1 is} C ¹ -C ₈ -alkyl, phenyl or a group - (CH ₂ ) _C -CO-OR ⁴ or -CH ₂ CH ₂ OR ⁹ , R ^{2 is} hydrogen, C ₁ -C ₁₈ -alkyl, phenyl, benzyl , or a group

^ -OH or - (CHz) ₀ -CO-OR "or -CH ₂ CH ₂ OR ⁹

means

R ³ C ₁ -C ₆ O-AIkYl, or one of the groups -CH-CH ₂ -SR ⁸

-CH ₂ -C-

-CH ₂ -OCCH ₀ , (y~ OH

b Zo \ /

is wherein Q Cj-Co-alkylene, C ₄ -C _e -Thiaalkylen or a group -CH ₂ CH ₂ (OCH ₂ CH ₂ JD, R ⁴ is C, -C ₂₄ alkyl,

R ^{6 is} hydrogen, C 1 -C ₁₈ -alkyl or cyclohexyl, R ^{e is} C 1 -C ₆ -alkyl, cyclohexyl, phenyl, C 1 -C ₈ -alkyl-substituted phenyl or one of the groups

• -0H

-C - (- (CH ₂ ) -OeC, H _, - f

D Δ0 \

^J 3

means

or R ⁵ and R ^e together are C 1 -C 5 -alkylene which may be interrupted by -O- or -NH-, R ^{7 is} hydrogen, C 1 -C ₄ -alkyl or phenyl, R ^{8 is} C 1 -C ₁₈ - Alkyl means

R ⁹ is hydrogen, Ci-C ₂ 4 alkyl, phenyl, C2-C ₈ alkanoyl or benzoyl, R ^'0 Q-Cie-alkyl, cyclohexyl, phenyl, C ₁ -C ₈ -alkyl-substituted phenyl or a group

- (CH ₂ ) -NH -CH ₂ -

B means

R "is hydrogen, C, -C ₁₈ alkyl, cyclohexyl, or a group

B means or

R ¹⁰ and R "together denote C 1 -C 4 -alkylene which may be interrupted by -O- or -NH-, a is 0, 1, 2, or 3,

b is 0,1,2 or 3,

c is 1 or 2,

d is 1 to 5,

f is 2 to 8 and

q is 1,2,3 or 4,

or as component (C) a mixture of polyphenols obtained by reaction of at least one phenol of the formula

V ¹¹ OH

c - / \ V \ / ^D

¹ J j or Il i

with at least one phenol of the formula

OH OH

Il I or IJ J

and with formaldehyde or paraformaldehyde, where C, D and E independently of one another are C ₁ -C 4 -alkyl, cyclohexyl or phenyl, the composition containing no aromatic amine.

In this composition, the weight ratio of (B) to (C) is preferably 1: 1 to 1: 100, especially 1: 3 to 1:20.

The sum of (B) and (C) is preferably 0.05 to 5 wt%, especially 0.1 to 3 wt%, of (A).

A and B as C, -C ₂₄ alkyl may be linear or branched alkyl, such as. Methyl, ethyl, i-propyl, t -butyl, s -butyl, s -pentyl, t -pentyl, n -hexyl, i -hexyl, t -hexyl, i-heptyl, n -octyl, t -octyl, s-decyl, s-dodecyl, n-dodecyl, s-tetradecyl, n-hexadecyl, n-octadecyl, s-octadecyl or n-eicosyl.

A and B as cycloalkyl may be e.g. Cyclopentyl, cyclohexyl or cyclooctyl, in particular cyclohexyl. A and B as phenylalkyl may, for. B. benzyl, phenylethyl, phenylpropyl or α, α-dimethylbenzyi be.

R ^s and R ⁶ as C | -C ₁₂ alkyl may, for. Methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, deryl or dodecyl. R ¹ , R ² , R ³ and R ⁸ as C, -C ₁₈ -AlkVl can also see, for example, tetradecyl, hexadecyl or octadecyl seh ;. In addition, R ⁴ as C ₁ -C ₂ 4-alkyl may also be, for example, eicosyl or tetra-eicosyl.

The index a is preferably 0.1 or 2, in particular 0 or 1; b is preferably 0.1 or 2, in particular 1 or 2; q is preferably 1 or 2, in particular 1.

The component (A) is a mineral or synthetic base oil, as is customary for the preparation of lubricants.

Synthetic oils may e.g. As esters of polycarboxylic acids or polyols, they may be aliphatic polyesters or poly-α-olefins, silicones, phosphoric acid esters or polyalkylene glycols. The lubricant may also be a grease based on an oil and a thickening agent. Such lubricants are z. B. in D. Klamann "lubricants and related products", Verlag Chemie, Weinheim 1982 described.

Component (8) may be any cyclic or noncyclic, preferably cyclic, hindered amine.

(B) is preferably a compound which contains at least one group of the formula II,

RCH ₂ P ^ *

-N ₁

RCH ₂ CH ₃

where R is hydrogen or methyl. Preferably, R is hydrogen. These are derivatives of polyalkylpiperidines, in particular 2,2,6,6-tiramethylpiperidine. Preferably, these compounds carry in the 4-position of the piperidine ring one or two polar substituents or a polar spiro ring system. These compounds may be low molecular weight or oligomeric or polymeric compounds.

Of particular importance are the following Klasson of polyalkylpiperidines. a) compounds of the formula III,

) - (

wherein η is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R ¹¹ is hydrogen, oxyl, hydroxyl, C, -C, _r alkyl, C ₁ -C ₈ alkenyl, Cj-Ce-alkynyl, C 1 -C ₆ aralkyl, C 1 -C ₁₈ alkoxy, C ₅ -C ₈ cycloalkyl, Cz-C 1 -C 4 phenylalkoxy, C 1 -C ₆ alkanoyloCaCe-alkenoyl, C 1 -Cis alkanoyloxy, benzyloxy, glycidyl or a group -CHjCH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R "is preferably H, C 1 -C 4 -alkyl, allyl, benzyl, acetyl or acryloyl and R ¹² , if η is hydrogen, optionally interrupted by one or more oxygen atoms C, -C _{) 8} alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic ^ araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical an aliphatic carboxylic acid having 2 to 18 C atoms, a cycloaliphatic carboxylic acid having 7 to 15 C atoms, a , β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, when η is 2, C, -C ₁₂ alkylene, C ^ -CirAlkenylen, xylylene, a divalent radical of an aliphatic , cycloaliphatic ^ araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C-atoms or an aliphatic, cycloaliphatic or aromatic Dicarbamic acid having 8-14 C atoms, when η is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical and when η is 4, a tetravalent radical of an aliphatic , cycloaliphatic or aromatic tetracarboxylic acid b edeutet.

Badeuten any substituents Ci-C ^ alkyl, they provide z. For example, methyl, ethyl, n-propyl, η-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, h nonyl, n-decyl, n-undecyl or n -Dodecyl is.

In the meaning of C 1 -C ₈ -alkyl, R 1 'or R' ^{2 may,} for example, represent the abovementioned groups and additionally, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If R "is C) -C ₈ -alkenyl, it may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2 -butenyl act.

R "as Cj-C ₈ -alkynyl is preferably propargyl.

As Cr-C, 2-aralkyl, R "is in particular phenethyl and especially benzyl.

R "is as Cp-Cs-alkanoyl, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C ₃ -C ₆ -AlkenoyI especially acryloyl.

If R ' ² denotes a monovalent radical of a carboxylic acid, it represents, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacylic acid, benzoic acid or β-fc3,5-di-tert-butyl-4-hydroxyphenyl. -prc.pione acid residue.

If R ' ² denotes a bivalent radical of a dicarboxylic acid, it represents, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid or BicycloheptendicarbonsÄureeste.

If R ' ^{2 represents} a trivalent radical of a tricarboxylic acid, it means z. B. a Trimellitsäure-, citric acid or nitrilotriacetic acid residue.

R ^{12 represents} a tetravalent radical of a tetracarboxylic acid, it means z. As the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or pyromellitic acid.

If R ' ^{2 is} a bivalent radical of a dicarbamic acid, it represents, for example, a hexamethylenedicarbamic acid or a 2,4-tolylene-dicarbamic acid radical.

Preference is given to compounds of the formula III in which R is hydrogen, R ¹ 'is hydrogen or methyl, η is 1 and R ^{12 is} C) -C | ₈ -alkyl or η is 2 and R ^{12 is} the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C atoms.

Examples of polyalkyl ^ -oeridine compounds of this class are the following compounds:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine

2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

3) 1 -8-Cyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine

5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine

6) 1-Ethyl ^ -salicyloyloxy ^^ e.e-tetramethylpiperidine

7) 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

8) 1,2,2,6,6-pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphilyl) propionate

9) di (I-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate

10) Di-tert-e-tetramethylpiperidine-y-succinate

11) di (2,2,6,6-tetramethylpiperidin-4-yl) -glutarate

12) di- (2,2,6,6-tetra-methylpiperidin-4-y-adipate

13) Di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate

14) di (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate

15) di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate

16) di (I-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

17) i-Hydroxy ^ -β-cyanoethyloxy ^ .e.e-tetramethylpiperidine

18) i-Acetyl ^^ e.e-tetramethylpiperidine ^ -yl-acetate

19) Trimellitic acid tri- (2,2,6,6-tetramethylpiperidin-4-yl) ester

20) i-AcryloyM-benzyloxy ^ -α-tetramethylpiperidine

21) diethylmonic acid di (2.2 _l 6 _{l of} 6-tetramethylpiperidin-4-yl) ester

22) dibutyl malonic acid di-d ^ Ae-pentamethyiplperidin ^ -yU-ester

23) Butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid di- (1,2,2,6,6-pentamethylpiperidin-4-yl) ester

24) di-fi-octyloxy ^^. E.-tetramethylpiperidine ^ -d-sebacate

25) Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

26) hexane-1 ', 6'-bis (4-carbamoyloxy-1-n-butyl-2,2,6 _/ 6-tetramethylpiperidine)

27) toluene-2 ', 4'-bis (4-carbamoyloxy-1-n-propyl-2,2, e _/ tetramethylpiperidine)

28) Dimethyl bis (2,2,6,6-tetramethylpiperidine-4-oxy) silane

29) phenyl-tr ^; s- (2,2,6,6-tetramethylpiperidin-4-oxy) silane

30) Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

31) Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

32) phenyl [bis (1,2,2,6,6-pentamethylpiperidin-4-yl)] - phosphonate

33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine

34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine

35) 4-hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine 36! 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpip8ridin

b) compounds of the formula IV,

RCHz _n / ^CH 3 / ^R

-Rl- IV

RCH ₂ ^{κ X} CH ₃

^Y n

in which η is the number 1 or 2, R and R "are the meanings given under a), R ^{13 is} hydrogen, C _t -C _t2 -alkyl, C ₂ -C ₆ -hydroxyalkyl, Cs-CT-cycloalkyl, CT-Ce -Aralkyl, Cy-C ^ alkanoyl, Cj-CB alkenoyl, benzoyi or a group of the formula

RCH - / ^N CH ₃

and R ^{14 is,} when η is 1, hydrogen, C ₁ -C ₈ -alkyl, C ₁ -C ₆ -alkenyl, C ₆ -C ₇ -cycloalkyl, C, -C substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group ₄ alkyl, glycidyl, a group of the formula -CHt-CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; when η is 2, C ₂ -C ₁₂ -alkylene, C ₁ -C 4 -arylene, xylylene, a -CHR-CHIOHJ-CHa group or a GrUpPe-CH ₂ -CH (OH) -CH ₂ -ODO-, wherein D is C 1 -C ₁₀ -alkylene, C 1 -C 4 -arylene, C 1 -C 4 -cycloalkylene, or provided that R ^{13 is} not alkanoyl, alkenoyl or benzoyl, R ^{14 is} also a bivalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or else the group -CO-, or R ¹³ and R ' ⁴ together, when η is 1, may denote the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2-odor 1,3-dicarboxylic acid.

If any substituents are C) -C ₁₂ - or C ₁ -C ₁₈ -alkyl, then they have the meaning already given under a).

If any substituents are Cs-Ct-cycloalkyl, they are in particular cyclohexyl.

As CT-Ce-aralkyl R ^{13 is} in particular phenylethyl or especially benzyl. As Cz-Cs-hydroxyalkyl R ^{13 is} in particular 2-hydroxyethyl or 2-hydroxypropyl.

R ' ³ as Cj-C ₁₈ alkanoyl, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as Cj-Cs-alkenoyl, in particular acryloyl.

If R ^{14 is} CHVA-alkenyl, then it is z. Allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R ¹⁴ as with a hydroxy, cyano, alkoxycarbonyl or carbamide substituted Ci-C ₄ -alkyl may, for. 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) -ethyl.

If any substituents represent C ₂ -C ₁₂ -alkylene, these are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

If any substituents Cs-C ₁₆ -arylene, they represent z. As o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene

As Ce-C ₁₂ -cycloalkylene D is in particular cyclohexylene.

Preference is given to compounds of the formula IV in which η is 1 or 2, R is hydrogen, R "is hydrogen or methyl, R ^{13 is} hydrogen, C) -C ₁₂ -alkyl or a group of the formula

RCH ₂ ^{7 N} CH ₃ and R ^u in the case of η = 1 is hydrogen or C, -Cj ₂ alkyl, and in the case of η = 2 C 2 -C ₈ -alkylene.

Examples of Polyalkylplperldln-Verblndungen this class are the following compounds:

37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine

38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide

39) Bis (2,2,6,6-tetramethylpiperidin-4-yl) amine

40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine

41) N, N'-bis (2,2,6, e-tetramethylpiperidin-4-yl) -N, N'-dibutyl-adipamide

42) N ,. '-Bis- (2,2,6,6-tötramethylplperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamino! I

43) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylenediamine

44) N, N'-bis (2,2,6,6-tetramethyl-piperidin-4-yl) -succin-diamide

45) N- (2,2,6,6-tetramethylpiperidin-4-yl) -β-aminodipropionic acid di (2,2,6,6-tetramethylpiperidin-4-yl) ester

46) The compound of the formula

CH ₃ , CH ₃

_t r_yu ι

CH ₃ -N ⁷ ^ '- N-CH ₂ -CH (OH) -CH ₂ -O

' ^N ch ₃ y \

CH ₃ - (Jl-CH ₃

η ι

CH ₃ CH ₃ /

N _n ^ '- N-CK ₂ -CH (OH) -CH ₂ -0

47) 4- {bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine

48) 4- (3-methyl-4-hydroxy-5-tert-butylbenzoic acid amido) -2,2,6,6-tetramethylpiperidine

49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

c) compounds of the formula V,

in which η is the number 1 or 2, R and R "are as defined under a) and R ¹⁶ , when η is 1, is C 1 -C 6 -alkylene or -hydroxyalkylene or C 1 -C 4 -cycloxalkylene, if π 2 is the group (-CH ₂ J ₂ C (CH ₂ -)? means.

When R ^{15 is} CHA alkylene or hydroxyalkylene, it represents, for example, ethylene, 1-methylethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.

As _C4-C22 acyloxyalkylene, R ^16, for example, 2-ethyl-2-acetoxymethylpropylene.

Examples of polyalkylpiperidin compounds of this class are the following compounds:

50) 9-A2a-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane

51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecane

52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane

53) g-Aza-S-hydroxymethyl-S-ethyl-e.e.S.IO.IO-pentamethyl-I.S-dioxaspiroiö.Slundecan

54) S-Aza-S-ethyl-S-acetoxymethyl-g-acetyl-e.e.iO.IO-tetramethyl-i-dioxaspirol S.Sjundecan

55) 2,2,6 _/ 6-T3-tramethyl-piperidine-4-spiro-2 '- (1', 3'-dioxane) -5'-spiro-5 "- (r, 3" -dioxane) -2 "-spiro -4 "'-(2"', 2 "',6"', 6 "'- tetramethylpiperidine).

d) compounds of the formulas VIA, VI B and VIC

R ¹¹ -N

X '

? = O

VIA

-R ¹⁷

R ¹¹ -K

VIB

R ¹¹ -

VIC

wherein η is the number 1 or 2. R and "have the meaning given under a), R ¹⁶ is hydrogen, C ₁ -C ₁₂ -alkyl, allyl, benzyl, glycidyl or Cj-C _e alkoxyalkyl and R" is, if η 1, is hydrogen, C ₁ - C ₁₂ alkyl, CH 2 alkenyl, cy-Cr aralkyl, C ₆ -C; Cycloalkyl, C ₂ -C 4 hydroxyalkyl, CH 3 alkoxyalkyl, C ₈ -C ₁₀ aryl, glycidyl or a group of the formula - (CH ₂ ) _p -COQ or the formula - (CH ₂ Ip-O-CO-Q wherein ρ is 1 or 2 and Q is C ₁ -C ₄ alkyl or phenyl when η is 2, C ₂ -C ₁₂ alkylene, C ₁ -C ₄ alkenylene, C ₆ -C ₁₂ arylene, a GrUpPe CH ₂ -CH (OHJ-CH ₂ -O-O-CH ₂ -CH (OH) -CHR-, wherein DC ₂ -C _{10 is} alkylene, Ce-C ₁₈ -arylene, C ₆ -C ₁₂ -cycloalkylene, or a group -CH ₂ CH ( OZ ') CH ₂ - (OCH ₂ -CH (OZ') CH ₂ ) _r -, wherein Z 'is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl, T is ₀ aryl or Cr-C ^ aralkyl, or T ₁ and T ₂ together with the | ₁ and T ₂ are independently hydrogen, Ci-C _1e alkyl or optionally halogen or C ₁ -C ₄ -alkyl substituted Ce-C they form a C _s -C ₁₂ cycloalkane ring.

If any substituents C) -C ₁₂ alkyl, so they provide z. For example, methyl, ethyl, n-propyl, η-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any substituents in the meaning of C 1 -C ₈ -alkyl may, for. As the above-mentioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl represent.

If any substituents C ^ Ce-alkoxyalkyl, so they provide z. For example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

R ^{17 represents} Ci-Cs-alkenyl, it means z. 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

As Cy-Ca-aralkyl R ¹⁷ , T ₁ and Tj, in particular phenethyl or especially benzyl. If T ₁ and T ₂ together with the C atom form a cycloalkane ring, this can be done, for example, by As a cyclopentane cyclohexane, cyclooctane or cyclododecane be.

If R ^{17 is} C ₂ -C ₄ -hydroxyalkyl, it is z. For example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As Cg-C ₁₀ -aryl R ¹⁷ , T ₁ and T ₂ , in particular phenyl, α- or ß-naphthyl, which are optionally substituted by halogen or C, -C ₄ alkyl.

If R ^{17 is} C ₂ -C ₁₂ -alkylene, this is z. For example, ethylene, propylene, 2,2-dimethylpropylon, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

As C ₄ -C 12 -alkenylene, R ^{17 is} in particular 2-butenylene, 2-pentenylene or 3-hexenylene.

If R ^{17 is} Ce-C 1-4 -arylene, it is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

If Z 'is C ₂ -C ₁₂ -alkanoyl, it represents, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

D has the meaning given under b) as C ₂ -C ₁₀ -alkylene, Ce-C _l6 -arylene or Cg-C ₁₂ -cycloalkylene.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

56) 3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5-decane-2,4-dione

57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5-decane-2,4-dione

58) 3-allyl-1,3,8-triaza-7,7,9,9-pentamethylspiro [4.5-decane-2,4-dione

59) 3-Glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-dione

60) 1,3,7,7,8,9,9-heptamethyl, 3,8-triazaspiro [4.5] decane-2,4-dione

61) 2-iso-propyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane

62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane

63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro | 5.1.H.2] -heneicosane

64) 2-Butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro [4,5] decane

65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4,5] -decane-2,4-dione or the compounds of the following formulas:

CH ₃ , CH ₃ -N,

xH

CH ₃ ⁷ NiH ₃

: = o o = c-N

N-CH ₂ CH (OH) CH ₂ - [OCH ₂ -CH (OH) CH ₂ ] ₂ -li

I r- ^7x

N-CH ₃ CH ₃

CH ₃

L_ NH-C = O

67) ^C "3- <X '

O = C-NH · ^ -

(CH ₂ )

-CH ₃

CH ₃ ^{7 X} CH ₃

CH ₃ ^{7 X} CH ₃

H-C = O

O = C-N

"---. %

CH ₃ ^{7 N} CH ₃

I, - t

CH ₃ ^{7 X} CH ₃

-CH ₂ CH ₂ COOCi ₂ H ₂₅

e) compounds of the formula VII,

_ _R 2 0

wherein η is the number 1 or 2 and R ' ^{8 is} a group of the formula

CH ₃ ⁷

where R and R "are as defined under a), EO- or -NR ²¹ -, A is Cr-Ce-alkylene or- (CH ₂ ) jO- andx are the numbers O ori, R ' ^{9 is} R ¹⁸ or one of the group NR ^2I R ", - OR ²³ , -NHCH ₂ OR ²³ or -N (CH ₂ OR ²³ ) ₂ , H ²⁰ if η = 1, R ¹⁸ or R ¹⁸ , and if η = 2, a group - EBE-, wherein B is optionally -N (R ² ') -interrupted Cr-C _e -alkylene, R "is Ci-Ci ₂ -alkyl, cyclohexyl, benzyl or C, -C ₄ -hydroxyalkyl or a group of the formula

CH ₂ R

CH ₃ ^{7 N} CH ₂ R

, R "is C ₁ -C) ₂ alkyl, cyclohexyl, benzyl, C ₁ -C ₄ hydroxyalkyl and R ²³ is hydrogen, Ci-Ci ₂ alkyl mean ODSR phenyl or R ²¹ and R ²² together are C ₄ -C ₆ alkylene or -Oxaalkylen, for example

O, or a group of the formula -CH ₂ CH ₂ ^/ -CH ₂ CH

or R ² 'and R ^{22 are} each a group of the formula

CH ₃ . , CH _{3 r} "\ / T ⁹ N

CH ₃ ^{7 N} CH ₃

• ·

CH / Y ^x CH ₃

mean.

If any substituents C ₁ -C ₁₂ -AIRyI, they represent, for example, methyl, ethyl, n-propyl, η-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n Nyl, n-decyl, n-undecyl or n-dodecyl.

If any substituents CHVHydroxyalkyl, so they provide z. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

If AC ₂ -C ₆ alkylene, it represents, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

R ²¹ and R ²² together represent C ₄ -Cs-alkylene or -oxaalkylene, this means z. As tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this class are the compounds of the following formulas:

H _{3 / C} H ₃

(CH ₃ CHz) ₂ N ⁷ \ ' N (CH ₂ CH ₃ )

_{/ C}H₃ \ CH_{3n / C}H₃

c ₂ h ₅ -n () -f V ΐ ^ - ⁷

ⁱ ^ ch ₃ ⁷ '\ h ₃

H ₃ C _n

·· ₇₂₎ N Jf with R = -NH-CH ₂ CH ₂ CH ₂ -O- _N ^ N-CH ₃

H ₃ C ⁷

rc / ro \ / I \ f / \ ro X I ro ro JC CJ CJ X K O O α O I / \ CM V χ L CJ X ⁵ F Y

ro ·

χ ι

CJ

/ \ • / ^u ro SC ro ic ° \ j I \ ΪΠ X CJ / j CJ Ϊ5 O CJ ro I I • CJ · cn

CJ

• 55 =

rc

CJ

CJ

I O X ro \ I * σ * CJ K CJ Ä / \ ΪΠ O \ ro O O η X V O \ / m O

75) R-NH- (CHz) ₃ -N- (CHz) z N- (CH ₂ ) ₃ -NH-R

with R

CH ₃ ^ -

Λ-ϊ ^ - · '>

CH ₉ -IjI

CH / Y ^x CH ₃

76) R-NH- (CHz) ₃ -N- (CHz) zN- (CHz) ₃ -NH-R

with R

A.

-A.

CH ₃ ' Ύ ^X CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

CH ₃ RR CH ₃

7 7) RN- (CHz) ₃ -N- (CHz) zN- (CHz) ₃ -NR

with R

.A.

- / ^ N-CH ₃

• - ·

cfi ₃ ^N CH ₃

CH / \ ^{y N} CH ₃ CH ₃

• ·

C ₈ Hi ₇ -IjI-

- Y Nj ⁷ \ h (ch ₂ ) 3

J i / \

CH,

CH ₃

CH ₂ CH ₂ OH

^CH \ Λ

JJl-CH ₉

_ny CH ₃

• - ·

HO-CH ₂ CH ₂ -l / / · -f

· - · C ₁₁ H ₉

CH ₃ CH ₃

CH ₃

C \ -CH2CH2-OH

H ₉ · · · (

CH ₃ CH ₃

CH ₂ -CH = CH ₂ X _{/ C} H ₃

A Ϊ.H ₃ / CH ₃

Π 2 Ο-MO-Π 2 »J-W,

H ₉ C

• t

CH3Z ^N CH ₃

f) oligomeric or polymeric compounds whose recurring structural unit contains a 2,2,6,6-tetraalkylpiperidine radical of the formula (I), in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly ( meth) acrylamides and their copolymers containing such radicals.

Examples of 2,2,6,6-polyalkylpiperidine light stabilizers of this class are the compounds of the following formulas, where m is a number from 2 to about 200.

⁸¹⁾ "" _{/ C} H ₃

Vo-4

m V

- ^ C-CH ₂ -CH ₂ -CO-CH ₂ -CH ₂ -N ⁷ ^ - Ol · -

^S CH ₃

pil OU Lni _v LH3 - \ CH ₃ O · - / CH ₃ C ₂ H ₅ JU ^ - (CH ₂ ) 1, -CJ- H ₂ -N ⁷ ^) - OI ! - (CH ₂ ) • I N-CH ₂ -CH ₂ -oi Un ₃ Ln ₃ CH ₃ ⁷ CH _3n ^, C ₂ H ₅ CH _3n ) , ' O \ # \ K T_' ~ j M Jni · -. t ³ \ / \ • ί N- (CH ₂ ) ₃ -ΝΗ-ί / \ C " V CH ₃ V \ 3 C2H5 CH ₃

CH ₃ ⁸⁴⁾ PH PH

yn ₃ yn ₃

NH-C-CH ₂ -C-CH ₃ , ' CH ₃ CH ₃

_N (CH ₂ ) 6-6

Ln ₃ . · T, 1,113 Ln ₃ . '' .LH ₃ \ l I / \ l I /

CH ₃ ⁷ N ^{7 N} CH ₃ CH ₃ ⁷ N ⁷ \ h ₃

-fN CH 2 -CH (OH) -CH ₂ +

CH _3n J ⁷ \ _{/ C} H ₃

• ·

CH ₃ ⁷ Y \ h ₃

CH ₃

-f-O- • ⁷ ^ N-CH ₂ -CH = CH-CH ₂ -N

CH ₃

.A.

- (CH ₂ ),

ι ϊ

CH ₃ ⁷ Y ^N CH ₃

CH ₃

Ο- · ⁷ N-CH ₂ -

* - ·

CH ₃ ^{7 X} CH ₃

CH ₃ ^{7 X} CH ₃

-O-CH ₂ -CH ₂ -N ^{7 X} - 7 & A-

CH ₃ ^{7 X} CH ₃

?Ha

O = C

-CH ₂ - ^ CH _3x / CH ₃

<> -CH ₃

CH ₃ ^{7 X} CH ₃

-CH ₂ -

O = C C ₆ H ₁₃ -N- '

CH ₃ CH ₃

-CH ₃

CH ₃ ^{7 X} CH ₃

⁹²⁾ A

• ·

I i

II / CH ₃ ⁷ Y ^X CH ₃ CH ₃ ⁷ Y ^X CH ₃

-f IjI (CH ₂ ) e IjI CH ₂ -CH ₂ -

CH ₃ ^ '/ N, CH ₃ CH _3v ; ^7X ; , CH ₃

I / \] I /

CH ₃ ^{7 X} jj ^{7 X} CH ₃ CH ₃ ⁷ Y ^X CH ₃

-f N (CH 2) 6 ti - C CH 2-

CH / Y ^x CH ₃ CH / Y ^x CH ₃

g) Compounds of the formula VIII, RCH _2x / CH3 / R

  ·

_R ii_ _N / \ = ₀ ' _{V |||}

RCH ₂ ^{7 X} CH ₃

wherein R and R "have the meaning given under a).

Preference is given to compounds of the formula VIII in which R is hydrogen or methyl and R "is hydrogen or methyl.

Examples of such compounds are:

95) 2,2,6,6-tetramethyl-4-piperidone (triacetonamine)

96) 1,2,2,6,6-pentamethyl-4-piperidone

97) 2,2,6,6-tetramethyl-4-piperidone-1-oxyl

98) 2,3,6-trimethyl-2,6-diethyl-4-piperidone

The polyalkylpiperidines are known compounds and are used as light stabilizers for organic materials. Some of them are available in stores.

Component (C) is a phenolic antioxidant. Preferably (C) is a compound of formula I, wherein A is hydrogen, Ci-Cg-alkyl, cyclohexyl, phenyl or a group

λ means

B is C 1 -C 6 -alkyl, cyclohexyl or phenyl, XC, -C _e -alkyl or one of the group-C, H ² , -SR ₂ , -CbH ₂ b-COOR ³ _/ -CH ₂ N (R ¹⁰ J (R ") or

-CH ₂ - ^ ^ - 0H

o means

R ^{2 is} C ₁ -C ₁₂ alkyl, phenyl or a group - (CHj) ₀ -COOR ⁴ , R ³ C, -C | _8- alkyl or a group

Έ is,

wherein UC ₂ -Ce-AIkYIe ^ -CHjCH ₂ SCH ₂ CH ₂ -or-CH ₂ CH ₂ (OCH ₂ CH ₂ ),! - means R ⁴ C, -C | _8- alkyl,

R ¹⁰ and R "independently of one another are C 1 -C ₁₂ -alkyl or R ¹⁰ and R" together are pentamethylene or 3-oxapentamethylene, a is 1 or 2, b is 1 or 2, c is 1 or 2 and d is 1 to 3 or (C) is a reaction mixture of a phenol of the formula

C-H

C-J

Il

with a phenol of the formula

_? H

E;

or

or

C-

_? H

/ V

-D

Il

and (para) formaldehyde, wherein C, D and E are independently C, -C ₈ alkyl.

A particularly suitable as component (C) class are the compounds of formula I, wherein A and B are independently C, -C4-alkyl, X is a group -C, H ₂ , -S _q -R ² , a O or 1 is, q is 1 or 2, R ^{2 is} C ₄ -C ₁₈ alkyl, phenyl

or-CH ₂ -CO-OR ⁴ and R ⁴ Ci-Cie-alkyl, in particular the compounds of formula I, wherein A and B are independently C ₁ -C ₄ -alkyl, X is -CH ₂ -SR ² , R ^{2 is} Cg-C ₁₂ -alkyl or -CH ₂ -CO-OR ⁴ and R ^{4 is} Cs-C ₁₈ -alkyl.

Especially preferred in this class are compounds of the formula I, wherein A and B are tert.Buiyl and X-CH ₂ SCH ₂ COO (C ₈ -C ₃ alkyl).

Another class which is particularly suitable as component (C) are the compounds of the formula I ₁ in which A and B, independently of one another, denote C ₁ -C ₄ -alkyl, X is a group -C _b H ₂ b -CO-OR ³ , b 1 or 2 and R ^{3 is} one of the groups

- (CH ₂ ) 2-S- (CH ₂ ) ₂ -OCC _b H _{2b N}

-OH

- (CH ₂ ) ₆ -O-ö-C _b H _2b () -OH

-CH ₂ -C-

• -0H

means,,

in particular the compounds of the formula I in which X is a group - (CH ₂ I ₂ -CO-OR and R is a group

- (CH ₂₎ ZS _(CH2) 2-0-C (CH ₂₎ -

Another class which is particularly suitable as component (C) are the methylene bisphenols of the formula (I) H (J) H

_CH2

HO

-CH ₂

< ^N

-OH

wherein A, B and X are independently C, -C ₄ alkyl.

Also particularly suitable as component (C) are mixtures of polyphenols, as obtained by reaction of at least one dialkylated phenol of the formula

(J) H (J) H

C \ \ C -. 'X-D

^υ Il I or Il I

V v

with at least one monoalkylated phenol of the formula _V H

or

y \

and formaldehyde or paraformaldehyde, where C, D and E independently of one another are C 1 -C ₄ -alkyl. The resulting mixtures contain mainly diphenols and triphenols.

Examples of compounds of the formula I are: tridecyl-4- (4-hydroxy-3,5-di-tert-butylphenyl) -3-thiabutyrate 3-thie-1,5-pentadiol-di [3- (4-hydroxybenzoyl) 3,5-di-tert-butylphenyl)] - propionate di (3-thiap8ntadecyl) -di (4-hydroxy-3,5-di-tert-butylphenyl) -malonate octadecyl-4- (4-hydroxy-3,5 -di-tert-butylphenyl) -3-thiabutyrate 4- (2-Thiapropyl) -2, b-di-tert-butylphenol Octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) - propionate 3-thiapentadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl-propionate di (4-hydroxy-3,5-di-tert-butylphenyD-sulfide di (4-hydroxy-3,5- di-tert-butylphenyll-disulfide 2,4-di (octylthiomethyl) -6-methylphenol

N-Octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionamide N, N '- [3- (4-hydroxy-3,5-di-tert-butylphenyl) -propionyl] hexamethylene -diamine 4,4'-methylenebis (2,6-di-tert-butylphanol) 2,2'-methylenebis (2-tert-butyl-4-methylphenol) 2,4-di (4-hydroxybenzyl) 3,5-di-tert-butylbenzyl) -6-tert-butylphenol 4,4'-Methylenebis [2-tert-butyl-4- (4-hydroxy-3,5-di-tert-butylbenzyl) phenol 4-Dimethylaminomethyl-2,6-di-tert-butylphenol 4-Dibutyiamino-methyl-2-methyl-6-tert-butylphenol N-di (4-hydroxy-3,5-di-tert-butylbenzyl-octylamine

Particularly preferred lubricant compositions are those wherein (B) is a compound of formula IX or X,

CH _{3 /} CHj

= 0

IX

wherein η is 1 or 2, R "is hydrogen or methyl and Y when η is 1, -O (CB-C ₁₆ -alkyl), and when π is 2, a group -NH- (CH ₂ ) J- NH- or -O-CO- (CHj) _1n -CO-O-, wherein m is 2-8, and

(C) is a compound of formula I, wherein A is hydrogen, C, -C ₄ alkyl or a group

means

BC _t -C ₄ alkyl,

X is C, -C ₄ alkyl or one of the groups -CH ₂ -SR ² , -CH ₂ CH ₂ COOR ³ , -CH ₂ N (R ¹⁰ I (R ¹¹ ) or

means

a ^{2 is} C ¹ -C 8 -alkyl, OdOR- (CH ₂ Ir-COOR ⁴ ,

R ³ C ₁ -C ₁₈ -AlkVl or

-C-CH ₂ CH ₂ - ". ⁷

-CH ₂ CH ₂ -S-CH ₂ CH ₂ -OC-Ch ₂ CH ₂ - * ^

means

R ^{4 is} C 1 -C ₁₈ -alkyl and

R ¹⁰ and R ^{11 are} Ct-Ca-alkyl, oaer (C) a reaction mixture of 2-tert. Butylphenol, 2,6-di-tert. butylpheno! and (para) formaldehyde.

Components (B) and (C) may be added directly to the base oil, or first dissolve (B) and (C) in a small amount of base oil, optionally with heating, and mix the solution with the remaining amount of OeI. One can also mix in a ι concentrated solution of (B) and (C) in a solvent to the oil.

The addition of (B) and (C) to the base oil stabilizes against oxidative degradation and causes a reduction in scum formation in engine oils.

The lubricant composition may additionally contain other additives, such as. Phosphorus III esters, metal deactivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, surfactants or / and anti-wear additives.

Examples of phosphorus esters are:

Triphenyl phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4 -di-tert-butylphenyl) -pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, bis (2,6-di-tert. butyl-4-methyl-phenyl) pentaerythritol diphosphite.

Examples of metal dosifactants, e.g. For copper, are:

Triazoles, benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenztriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidene propylenediamine, salicylaminoguanidine and its salts.

Examples of rust inhibitors are:

a) Organic acids, their esters, metal salts and anhydrides, e.g., N-oleoyl sarcosine, sorbitan mono-oleate, lead naphthenate, alkenyl succinic anhydride, e.g. Dodecenylsuccinic anhydride, alkenylsuccinic acid partial esters and -partamides, 4-nonylphenoxyacetic acid.

b) Nitrogen-containing compounds, for example:

I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, eg. B. oil soluble alkyl ammonium carboxylates.

II. Heterocyclic compounds, eg. B.: Substituted imidazolines and oxazolines.

c) Phosphorus-containing compounds, e.g.

Amine salts of phosphoric acid partial esters or phosphoric acid partial esters, zinc dialkyldithiophosphates.

d) Sulfur-containing compounds, for. B.: Barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates.

Examples of viscosity index improvers are:

Polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.

Examples of pour point depressants are:

Polymethacrylate, alkylated naphthalene derivatives.

Examples of di-excipients / surfactants are:

Polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium, and barium sulfonates and phenates.

Examples of precursors add.tlve are; Sulfur and / or phosphorus and / or halogen-containing compounds, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl di- and tri-sulfides, triphenyl phosphorothioates, diethanolaminomethyltolyl triazole, di (2-ethylhoxyl) u.Tiinomethyltolyltriazol.

The lubricant may also contain solid lubricants, such as. As graphite or molybdenum sulfide.

The following examples illustrate the invention in more detail. Therein mean% by weight.

Example 1:

The oxidation behavior of lubricating oils stabilized according to the invention is tested according to the TOST method (turbi.o oxidation stability test) according to ASTM D-943.

For this purpose, 300 ml of a mineral oil (Mobil STOCK305) containing 0.05% of a corrosion inhibitor (Reocor ⁸ 12), mixed with 60ml of water and heated in the presence of ice ·) and copper wire while passing oxygen for 1000 hours at 95 ° C.

The formation of acids is measured by determining the neutralization number TAN (mg KOH / g oil) and the amount of sludge = SLUDGE formed.

As stabilizers are used;

• - ·

P-1 HO- ^ ^ -CH ₂ -S-CH ₂ -COOCi ₃ H ₂₇

CH ₃

, CH ₃

H-1 HN J, OCi ₂ H ₂₅

• ·

CH ₃ CH ₃

The total amount of stabilizers is 0.25%, based on the oil. The composition of the stabilizer mixture is varied. The results are shown in Table 1.

Table 1

proportion of H-1 TAN TOST P-1 - 0.19 SLUDGE 100% 5% 0 64 mg 95% 10% 0 17 mg 90% 25% 0 8 mg 75% 26 mg

Example 2

It is tested as in Example 1. As stabilizers are used:

(CH _{3) 3} C

P_2 HO- ^ ^ - CH ₂ CH ₂ COOCH ₂ CH ₂ SCH ₂ CH ₂ OOCchzCH ₂ - ' ⁷

3H ₃ CH ₃ CH ₃ CH ₃

^X C (CH ₃ ) ₃

H-2 CH ₃ -N ^ OOC- (CHz) ₈ -COC- -CH ₃

CH ₃ CUi \ h ₃

The total concentration is 0.25%, based on the oil.

Table 2

Share TOST PJ H-2 JAN SLUDGE

100% ->2> 1000mg 95% 5% 0.26 219 mg 90% 10% ΓΛ24 190 mg

Example 3

It is tested as in Example 1. As stabilizers are used:

S / C (CH ₃ ) ₃

p.2 HO - _N - '- CH ₂ CH ₂ COOCH ₂ CH ₂ SCH ₂ Ch ₂ OOCCH ₂ CH ₂ - _N /' - 0H

CC (CH ₃ ) j

CH ₃ CH ₃ CH ₃ CH ₃

H <, NH (CH _{z) 6} -NH- \ .NH

Ch ₃ CH ₃ CH ₃ CH ₃

The total concentration is 0.25%. The results are shown in Table 3.

Table 3

Share TOST P-2 H-3 TAN SLUDGE

100% -> 2> 1000mg

95% 5% 0.24 180 mg

Example 4

It is tested as in Example 1. As stabilizers are used:

(CH _{3) 3} C _X P-2 HO _N ^ '- CH ₂ CH ₂ COOCH ₂ CH ₂ SCH ₂ CH ₂ OOCCH ₂ Ch ₂ - _N / ·

^N C (CH ₃ ) ₃

CH ₃ , CH ₃

H-1 HN ^ OCi ₂ H ₂₅

CH ₃

The total concentration is 0.25%. The results are shown in Table 4. Table 4

proportion of H-1 TAN TOST P-2 - > 2 SLUDGE 100% 5% 0 I 000 mg 95% 15% 0.10 86 mg 85% 25% 0.03 44 mg 75% 75 mg

Example 5

It is tested as in Example 1. As stabilizers are used:

/ \ P-2 HO- _χ ^ -CH ₂ CH ₂ COOCH ₂ CH ₂ SCH ₂ CH ₂ OOCCH ₂ Ch ₂ -

(CHjhC ⁷

C (CH ₃ )

CH ₃ The total concentration is 0.25%. The results are shown in Table 5.

Table 5

Share P-2

H-4

TAN

TOST

SLUDGE

5% 10%

> 2

0.18 0.16

> 1000mg

91 mg

161 mg

Examples

The oxidation resistance of the oils stabilized according to the invention is measured in a differential scanning calorimeter.

Here, in a Al-bowl a base oil with 0.025% ferric acetylacetonate (as an oxidation catalyst) and 0.55% of a Stabilisato · s and is mixed in the calorimeter under 10bar oxygen isothermally heated to 160 C ^J. The time until the beginning of the exothermic reaction Tb (induction time) and the time until the end of the exothermic reaction T _E is measured. The longer the induction time, the higher the oxidation resistance. The stabilizers used are the phenolic antioxidants P-1 and P-2, and:

P-3: reaction product of 160g 2,6-di-teit. bulylphenol, 40g of 2-tert-butylphenol, 5.8 g KOH, 50 ml of ethanol and 24 g of paraformaldehyde at 80 ⁰ C, comprising as main components

(CH _{3) 3} C

CH ₂

C (CH ₃ ):

C (CH ₃ ) 3

(CH ₃ )

HO

-CH ₂ -

: h ₂ -

Ύ \) Η C (CH ₃ ) ₃

, C (CHj) ₃ S-OH C (CH ₃ ) 3

(CH ₃ ) _3C .

HO- (CHj) ₃ C

-CH ₂ -

Il

YA

-CH ₂ -

Il

^0H

γ OH C (CH ₃ ) ₃

C (CH ₃ )

-OH

C (CH ₃ ):

OH OH

p. ^. ν ^ n ₃ ^ ₃ C-j · CH ₂ jj j-C (TH ₃ ) ₃

C (CH ₃ ) ₃ C (CH ₃ ) ₃

P-5: mixture 1: 1 of

OH OH

(CHs) ₃ CJ ^{7 X} '-C (CH ₃ ) ₃ and J ^XX ' -C (CH ₃ ) ₃

C (CHa) ₃ C (CH ₃ ) ₃

As hindered amine is used

C ^ _{3 /} CH ₃ CH ₃ CH ₃

The results are shown in Table 6.

Table 6

stabilizer T _B (min) Te (min) 0.55% P-1 1.47 9.12 0.55% H-5 17.16 22.97 0.45% P-1 + 0.10% H-5 14.02 27.71 0.55% P-2 16.08 26.07 0.55% H-5 17.16 22.97 0.45% P-2 + 0.10% H-5 32.27 47,90 0.55% P-3 7.21 14,20 0.55% H-5 17.16 22.97 0.45% P-3 + 0.10% H-5 50.55 67.97 0.55% P-4 3.00 9.67 0.55% H-5 17.16 22.97 0.45% P-4 + 0.10% H-5 12.02 20.37 0.55% P-5 4.46 16.44 0.55% H-5 17.16 22.97 0.45% P-5 + 0.10% H-5 14.10 23.23

It can be seen that when using Stabilisaxorgemischen from 0.10% of component A and 0.45% of component B, the oxidation resistance 'it is higher oil than would be expected from the data of the individual components

Example 7

The oxidation resistance is tested as in Example 6 in a differential scanning calorimeter, with the difference that instead of under 8 bar air, the 380ppm (NO) _x are mixed, measured and that the isothermal temperature is 170 ° C. Only the beginning of the exotherm is measured.

stabilizer Tb (min) u, 55% P-2 0.55% H-5 0.45 o / oP-2 + 0.10% H-5 11.2 <2 20,7 0.55% P-6 0.55% H-5 0.45% P-6 + 0.10% H-5 3.8 <2 10.8

P-6 HO- '(

Claims (19)

A lubricant composition containing (A) a mineral or synthetic oil or a mixture of such oils, (B) at least one sterically hindered amine and (C) at least one phenol of the formula I, wherein A is hydrogen, C ₁ -C ₂₄ alkyl, Cs-C ^ cycloalkyl, Cy-Cg-phenylalkyl, phenyl or a group -CH ₂ -SR ¹ or OH BC ₁ -C ₂₄ -alkyl, C ₁ -C ₁₂ -cycloalkyl, cyCg-phenylalkyl, phenyl or a group -CH ₂ -SR ¹ , X is hydrogen, C ₁ -C ₁₈ -alkyl or one of the groups C _a H _2a -S _q -R ² , -C _b H _2b -CO-OR ³ , -C _b H _2b -CO-N (R ⁵ ) (R ⁶ ), -CH ₂ N (R ¹⁰ KR ¹¹ ) or -CH ₂ - · ~ 0Η means R ^{1 is} C ₁ -C ₁₈ -alkyl, phenyl or a group- (CH ₂ ) C-CO-OR ⁴ or -CH ₂ CH ₂ OR ⁹ , R ^{2 is} hydrogen, C ₁ -C ₁₈ -alkyl, phenyl, benzyl or a group • - * -J V-OH or - (CH ₂ ) -CO-OR "or -CH ₂ CH ₂ OR ⁹ \ / ^c means R ⁷ R ^{3 is} C ₁ -C ₅₀ alkyl or one of the groups -CH-CH ₂ -SR ⁸ • -0H or -CH ₂ -C- CH ₂ -OCCH ₀ , «f Dio \ in which Q is C ₂ -C ₈ -alkylene, C ₄ -C ₆ -thiaalkylene or a group -CH ₂ CH ₂ (OCH ₂ CH ₂ ) d -, R ⁴ signifies C, -C ₂₄ -alkyl, R ⁵ denotes hydrogen, C ₁ -C ₁₈ -alkyl or cyclohexyl, R ^{6 is} C, -C ₁₈ -alkyl, cyclohexyl, phenyl, phenyl substituted by C ₁ -C ₁₈ -alkyl or one of the groups ~ OH -0H - (CHz) -OCC ₁ H ₀ , - b 2b \ / / -OH or R ⁵ and R ⁶ together are Gj-Ca-alkylene which may be interrupted by -O- or -NH-, R ^{7 is} hydrogen, CH-alkyl or phenyl, R ^{8 is} C ₁ -C ₁₈ -alkyl, R ^{9 is} hydrogen, C ₁ -C ₂ ^ AlkYl, phenyl, C ₂ -C ₁₈ alkanoyl or benzoyl, R ^{10 is} C ₁ -C ₁₈ alkyl, cyclohexyl, phenyl, phenyl substituted by C ₁ -C ₁₈ alkyl or a group - (r.] ₂ ) _f -NH -CH ₂ - ^ ^ • - · Έ means R ^{11 is} hydrogen, C ₁ -C ₁₈ alkyl, cyclohexyl, or a group -CH ₂ - means or R ¹⁰ and R ¹¹ together represent C ₄ -C ₈ -alkylene which may be interrupted by -O-or -NH-, a is 0,1,2 or 3, b is 0,1,2 or 3, c is 1 or 2, d is 1 to 5, f is 2 to 8 and q is 1,2,3 or 4, or as component (C) a mixture of polyphenols obtained by reaction of at least one phenol of the formula OH or ? VV Il with at least one phenol of the formula OH
M ι or OH
/ X Il and formed with formaldehyde or paraformaldehyde, where C, D and E independently of one another C ₁ -C ₂₄ -AIlCyI, cyclohexyl or phenyl, wherein the composition contains no aromatic amine. A composition according to claim 1, wherein the weight ratio of (B) to (C) is 1: 1 to 1: 100. A composition according to claim 1, wherein the weight ratio of (B) to (C) is 1: 3 to 1:20
is. A composition according to claim 1, wherein the sum of (B) and (C) is 0.05 to 5% by weight of (A). 5. A composition according to claim 1, wherein (B) is a compound containing at least one group of formula II, RCH ₂ / ^{CH 3} / ^R ₄ 1 - <XRCH ₂ CH ₃ wherein R is hydrogen or methyl. 6. A composition according to claim 5 wherein (B) is a compound containing at least one group of formula II wherein R is hydrogen. 7. A composition according to claim 5, wherein (B) is a compound of formula III, R ¹¹ -K -0 R CH ₃ III wherein R is hydrogen, R ^{11 is} hydrogen or methyl, η is 1 and R ^{12 is} C ₁ -C ₁₈ -AIRyI or η is 2 and R ^{12 is} the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C atoms.
8. A composition according to claim 5, wherein (B) is a compound of formula IV, RCH ₂ / CH _{3 /} RR ¹¹ - / ^ - RCH 2 ^{/ N} CH ₃ IV wherein η is 1 or 2, R is hydrogen, R ^{11 is} hydrogen or methyl, R ^{13 is} hydrogen, C, -C ₁₂ alkyl or a group of the formula RCH _z ^{y N} CH ₃ and R ^{14 is} hydrogen or C ₁ -C ₁₂ alkyl in the case of η - 1, and in the case of η = 2 C ₂ -C ₈ alkylene. 9. A composition according to claim 5, wherein (B) is a compound of formula VIII, ^Rll - <> ⁼ ° viii wherein R is hydrogen or methyl and R ^{11 is} hydrogen or methyl. 10. A composition according to claim 1, wherein (C) is a compound of the formula I wherein A is hydrogen, C ₁ -C ₈ -alkyl, cyclohexyl, phenyl or a group _? H -CH ₂ - jB means BC ₁ -C ₈ -AikyI, cyclohexyl or phenyl, XC ₁ -C ₈ -AIRyI or one of the groups -C _a H _2a -SR ² , -C _b H ₂ b COOR ³ , -CH ₂ N (R ¹⁰ J (R ¹¹ ) or means R ^{2 is} C ₁ -C ₁₂ -AIRyI, phenyl or a group - (CH ₂ ) _C -COOR ⁴ , R ^{3 is} C ₁ -C ₁₈ -alkyl or a group • - · -Q-OOC-C, H -, - f ^ is -OH, D iO N / • = s · wherein Q is C ₂ -C ₆ -alkylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -OdOr-CH ₂ CH ₂ (OCH ₂ CH ₂ ) (T, R ^{4 is} C ₁ -C ₁₈ -alkyl, R ¹⁰ and R ^{11 are} independently C ₁ -C ₁₂ -AIRyI or R ¹⁰ and R ¹¹ together are pentamethylene or 3-oxapentamethylene, a is 1 or 2, b is 1 or 2, c is 1 or 2 and d 1 to 3, or wherein (C) is a reaction mixture of a phenol of the formula OH? H * -Λ 'or ° fV with a phenol of the formula OH OH A A Il I or Il I and (para) Fon.ialdehyd, wherein C, D and E are independently C ₁ -C ₈ -AIRyI. A composition according to claim 1, wherein (C) is a compound of the formula I in which A and B independently of one another are C ₁ -C ₄ -alkyl, X is a group -C _a H _2a -S _q -R ² , a is O or is, q is 1 or 2, R ^{2 is} C ₄ -C ₁₈ -alkyl, phenyl or -CH ₂ -CO-OR ⁴ and R ^{4 is} C ₁ -C ₁₈ -alkyl. 12. A composition according to claim 1, wherein (C) is a compound of formula I wherein A and B are independently C 1 -C ₄ alkyl, X is -CH ₂ -SR ² , R ^{2 is} C ₈ -C ₁₂ alkyl or -CH ₂ -CO-OR ⁴ and R ^{4 is} C ₈ -C ₁₈ -alkyl. 13. A composition according to claim 1, wherein (C) is a compound of formula I wherein A and B are independently C ₁ -C ₄ alkyl, X is a group -CbH ₂ O-CO-OR ³ , b is 1 or 2 and R ^{3 is} one of the groups - (CH ₂ ) 2-S- (CH ₂ ) ₂ -O-O-C _b H _2b ^ ρ-OH - (CH ₂ ) 6 -OCC, H b 2b / -OH -CH ₂ -C- -CH ₂ OCC ₁ H ₀ , - b ΔΌ -OH ^J 3 means. A composition according to claim 1 wherein (C) is a compound of formula I wherein A and B are independently C ₁ -C ₄ alkyl, X is a group - (CH ₂ J ₂ -CO-OR ³ and R ³ a group - _(CH2) 2-S- _(CH2) 2-0-C- _(CH2) 2- means. 15. A composition according to claim 1, wherein (C) is a compound of formula OH OH ^Β Ίι } - ° ^Η2 ~ _# τ * or HO CH ₂ - -OH in which A, B and X independently of one another are C ₁ -C ₄ -alkyl. 16. The composition according to claim 15, wherein A, B and X tert. Butyl are. 17. A composition according to claim 1, wherein (C) is a mixture of polyphenols obtained by reacting at least one dialkylated phenol of formula or with at least one monoalkylated phenol of the formula oh y » or and formaldehyde or paraformaldehyde, where C, D and E independently of one another C ₁ -C ₄ -AlkYl mean. 18. A composition according to claim 17, wherein C, D and E tert. Butyl are. 19. Compositions according to Claim 1, in which (B) is a compound of the formula IX or X, R ¹¹ -K qj _{3 /} CH ₃ \ CH _{3 3} ^X CH ₃ cfi ^x IX wherein η is 1 or 2, R ^{11 is} hydrogen or methyl and Y, when η is 1, -O (C 8 -C ₁₅ -alkyl), and when η is 2, a group -NH- (CH ₂ ) O- NH- or -O-CO- (CH ₂ ) _m -CO-O-, wherein m is 2-8, and
(C) is a compound of formula I, wherein A is hydrogen, C ₁ -C ₄ -A ^ yI or a group C-H means BC ₁ -C ₄ -AlkVl means XC ₁ -C ₄ -AlkYl or one of the groups -CH ₂ -SR ² , -CH ₂ CH ₂ COOR ³ , -CH ₂ N (R ¹⁰ J (R ¹¹ ) or means R ^{2 is} C ¹ -C ₁₈ alkyl or (CH ₂ ) Z COOR ⁴ , R ^{3 is} C ₁ -C ₁₈ alkyl or -CH ₂ CH ₂ -S-CH ₂ CH ₂ -O-CH ₂ CH ₂ - ^{1 1} ^ means R ^{4 is} C ₁ -C ₁₈ alkyl and R ¹⁰ and R ^{11 are} C ₁ -C ₈ alkyl, or (C) a reaction mixture of 2-tert. Butylphenol, 2,6-di-tert. butylphenol and (para) formaldehyde. A composition according to claim 19 wherein (B) is a compound of formula IX wherein η is 2 and Y is a group -NH- (CH ₂ J ₆ -NH- or -O-CO- (CH ₂ ) 8-CO Is -0, and (C) the compound of the formula / C (CH ₃ ) 3 • - «· - · HO- _χ ^ -CH2CH2.COOCH2CH2SCH2CH2OOCCH2CH2- _χ / -OH (CH _{3) 3} C ^/ \ (CH _{3) 3} is.
2 \ Use of a composition according to claim 1 as a motor oil. 22. Use of a combination of (B) and (C) as defined in claim 1, for the stabilization of lubricants against their oxidative degradation. 23. Use according to claim 22 for reducing sludge formation in engine oils.