JPH0345695A - Lubricating agent composition - Google Patents

Abstract

PURPOSE: To obtain a lubricant compsn. stabilized against the collapse of oxidation induction without using an aromatic amine or phenolic oxidation inhibitor by compounding a mineral oil or synthetic oil with a specific sterically hindered amine.

CONSTITUTION: A lubricant compsn. consists of a mineral oil, a synthetic oil or a mixture of them (A) and a sterically hindered amine (B) represented by formula I being an oxidation preventing stabilizer but does not contain an aromatic amine and a phenolic oxidation inhibitor. In the formula I, n is 1 to 2, R is H or methyl, R₁ is H or a 1-12C alkyl, R₂ is H, a 1-12C alkyl or a group represented by formula II, R₃ is H or a 1-18C alkyl when n is 1 and a 2-12C alkylene or xylene when n is 2, R₄ is H or a 1-12C alkyl, R₅ is H or a 1-12C alkyl and R₆ is a 1-20C alkyl, 1-12C alkoxy or phenyl.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to lubricant compositions stabilized with I- against oxidation-induced degradation. Stabilization is achieved by adding sterically hindered amines of specific structure.

(Prior Art 1 Problem to be Solved by the Invention) In a lubricant based on mineral oil or synthetic oil.

It is known and customary to incorporate fA additives to improve their performance properties. Additives that suppress the oxidation-induced breakdown of lubricants, so-called antioxidants, are of particular importance. Oxidation-induced breakdown of lubricants can occur due to the high temperatures common in engine combustion chambers and due to the presence of nitrogen oxides (NOx), which act as oxidation catalysts in addition to oxygen. This is a particularly important factor.

Organic sulfur D and phosphorus compounds are particularly used as antioxidants in lubricants, as are aromatic amines and phenols, especially sterically hindered phenols. ,
(See, UllmanhsEncyclopMdie
dot technischen Chemie, 4
th edition.

Verlag Chemle, Vol, 20(19
81); 5at-s4s u) * i * For example, the use of sterically hindered amines to stabilize lubricants is proposed in U.S. Pat. has been done.

European Patent Application No. 1IC0556677 Fi calls for the use of mixtures of aromatic amines and sterically hindered amines as antioxidants in lubricating oils. Phenolic antioxidants can also be added to the mixture.

SUMMARY OF THE INVENTION The present inventors have now demonstrated that certain sterically hindered amino acids 7 can be used by themselves, i.e. without aromatic amines or phenolic antioxidants, to lubricate against oxidation-induced degradation. found that it is particularly suitable for stabilizing.

Specifically, the present invention is: (4) Mineral oil 1 synthetic oil or a mixture of these oils, D and @ 1 formula l as an antioxidant stabilizer (In the formula, n represents 1 or 21.

R represents a hydrogen atom or methyl Mt-.

RIFi hydrogen atom, alkyl group having 1 to 12 carbon atoms, allyl M, benzyl group, -Co-R4゜-OR@
Or represents -o-co-a.

R3 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a hydroxyalkyl group having 2 to 5 carbon atoms, or a group represented by the formula (2).

When RlH,n is 1f: a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a hydroxyalkyl group having 2 to 5 carbon atoms.

represents an alkoxyalkyl group having 3 to 18 carbon atoms or a dialkylaminoalkyl group having 4 to 20 carbon atoms, and when n represents 2, a group having 2 carbon atoms;
to 12 alkylene groups, 2-hydroxy-1,3-
Represents a globylene group or a xylylene group.

R4 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.

R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a benzyl group, and R6 represents an alkyl group having 1 to 12 carbon atoms.

The present invention relates to a lubricant composition comprising a sterically hindered amine represented by C1-C12 alkoxy group or phenyl IfI, but containing no aromatic amine and no phenolic antioxidant.

R,,R, having 1 to 12 carbon atoms.

R4, R, or R is a straight or branched alkyl group,
If kept, methyl, ethyl, and propyl groups.

Isopropyl group, butyl group, inoamyl group.

Hexyl M1 can represent heptyl M, an octyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group. , Rs n as C 1 -C 18 alkyl group and furthermore.

Tetradecyl group, hexadecyl group or octadecyl group
- can be expressed. R,, R, as alkyl group
, Rs or an unbranched alkyl group having 1 to 4 carbon atoms.

R as C5 -C12 cycloalkyl group
,, R3i tjR1tj cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cyclooctyl group or Schiff. It can represent a dodecyl group. A preferred meaning is cyclohexyl.

R3 or R3 as C2-C5 hydroxyalkyl group can be 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group or #'
i2-Hydroxybutyl group can be represented. The basic meaning is 2-hydroxyethyl group.

Rltf as an alkoxyalkyl group having 5 to 18 carbon atoms, 2-methoxyethyl group, 2-ethoxyethyl group, 5-methoxypropyl group, 5-ethoxyglobyl group, 3-ingloboxybrobyl group, 3 -butoxypropyl M or a 3-dodecyloxyglobyl group.

R11d as C4 -C20 dialkylaminoalkyl group, 2-dimethylaminodityl group, 5-
It can represent a diethylaminopropyl group, a 3-di(inoprobil)aminopropyl group or a 5-di(octyl)aminopropyl group.

R6 as C1 -C12 alkoxy is C1 -C4 alkoxy, most preferably methoxy M or ethoxy.

83 as C2 -C12 alkylene can be straight-chain or branched.

and 1 represents, for example, G-tri, tetra-, hexa-octa-, deca- or dodecamethylene, the 2,2-dimethyl-1,3-propylene group or the 2,2-dimethyl-4-methyl-hexamethylene group. .

Components preferably have the formula l (wherein n represents 1 or Fi2, R represents a hydrogen atom, and R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

It represents an allyl group, a benzyl group, an acetyl group, or -OR,@, R1 represents a hydrogen atom, a C1-C4 alkyl group, or a group represented by 2, RlFi,
When n represents 1, it is a hydrogen atom.

C1-C8 alkyl group or C5
and when n represents 21-, it represents an alkylene group having 2 to 8 carbon atoms, and f4. su an alkyl group having 6 to 10 carbon atoms.

This is a compound represented by ), which represents a cyclohexyl group or a benzyl group.

Most clearly, the ingredients are the formula! (In the formula, n is 1 or 2
and R represents a hydrogen atom.

R+1 represents a hydrogen atom, a methyl group or an acetyl group, R represents a hydrogen atom, and) Ll represents a hydrogen atom box or an alkoxyalkyl group having 3 to 8 carbon atoms, , and when n represents 2, a cycloalkylene group having 2 to 6 carbon atoms t-
It is a compound represented by ).

Further, the component () is a compound represented by formula 1 (in the formula, n represents 2, and R, #i represents an alkylene resin 2f having 2 to 6 carbon atoms).

Compounds of Formula I are described in U.S. Pat. No. 56,847
No. 65, No. 1!3904581 and No. 41042
This is a known compound disclosed in No. 48. These are used as light stabilizers for organic polymers.

Representative sequences of individual compounds of formula I are as follows.

2,2.6.6-Tetramethyl-4-butylaminopyridine.

2,2.6.6-Tetramethyl-4-octylaminopiperidine.

2,2.6.6-Tetramethyl-4-cyclohexylaminoviveridine.

2,2.6.6-Titramethyl-4-(N-hydroxyethylbutylamino)piperidine 2,2.6.6-Titramethyl-4-(3-methoxypropylamino)piperidine 2,2.6.6-Titramethyl-4- (3-dimethylaminopropylamino)piperidine.

Bis(2,2,6,6-tetramethylbiperidine-4-
yl)amine 2.3.6-drimethyl-2.6-ethyl-4-isoglobylaminoviveridine.

1.2.2.6.6-bentamethyl-4-dodecylaminopiperidine.

1,2.2.6.6-bentamethyl-4-(N-methyldodecylamino)piperidine 1-acetyl-2,2,6,6-tetramethyl-4-butylaminopiperidine.

1, 2. S, 6-tetramethyl-2,6-dinityl-4-(3-ethoxypropylamino)piperidine.

1-octyloxy-2,2,6,6-tetramethyl-
4-Hexylaminopiperidine.

1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-cyclohexylaminopiperidine.

N,N'-bis(2,2,6,6-tetramethylbiveridin-4-yl)-1,2-cya zeta-noethane.

N,N'-bis(2,2,6,6-tetramethylpipericin-4-yl)-hexamethylenediamine.

N,N'-bis(1,2,2,6,+6-bentamethylbiperidin-4-yl)-hexamethylenediamine.

N,N'-bis(1-acetyl-2,2,6,6-tetramethylbiperidin-4-yl)hexamethylenediamine.

N,N'-bisC1-benzyl-2,2,6,6-tetramethylbiperidin-4-yl)-m-xylenediamine, N,N'-bis(1-octyloxy-2,2° 6.6
-tetramethylpiperidin-4-yl)-2-human ax-1,5-diaminopropane.

Component (4) is a mineral or synthetic oil commonly used for the production of lubricating oils. The synthetic oil may be a polycarboxylic acid ester or a polyol ester;
or aliphatic polyester 4L<ayj (leave-olefin, silicone).

The lubricant may be a phosphate ester tube or a polyalkylene glycol, and the lubricant may be a fat based oil and thickener, such as:
D, ni1an+ann″8ehmi*rstoff*u
nd art vervrandte product
” (I15 lubricants and related products), Verlag
Chemie, Weinheim 1982.

Component (B) is added to the Fi pace oil in an amount of LO5 to 5% by weight, most preferably 1 to 2% by weight, based on the tube or base oil.Addition can be made directly;
Alternatively, first prepare a concentrated solution of the solution in the oil or another solvent and add this solution to the oil.

Any addition to the base oil stabilizes the oil against oxidation-induced breakdown and reduces sludge formation on carrot oil.

The lubricant composition may further include other additives such as phosphorus (II).
I) Ester, metal deactivator, rust inhibitor, viscosity index improver,
Pour point depressants 1 may contain dispersants, surfactants or antiwear agents.

Representative examples of phosphorus (m value) esters are as follows. Nitriphenylphosphite, decyltriphenylphosphite, phenyldidecylphosphite.

Tris (nonylphenyl) phosphite, trilauryl phosphite, trioctyldecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (
2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, tris(stearylsorbitol) triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite.

Bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite.

For copper, a typical sequence of metal deactivators is as follows. Nitriazole, penztriazole and its derivatives, tolutriazole and its derivatives, 2-mercaptobenzothiazole 2-mercaptobenzotriazole.

2.4-dimercaptobenzotriazole, 2゜5-dimercaptobenzothiadiazole, 5゜5-methylenebisbenzotriazole, 4.5゜6.7-titrahydrobenzotriazole, salicylidenepropylene diamine, salicylaminoguanidine and That salt.

The sequence of rust inhibitors is as follows: : a) Organic acids, their esters, metal salts and acid anhydrides, such as diN-oleylsarcosine, sorbitamonooleate, lead naphthalate.

Alkenylsuccinic anhydride such as dodecenylsuccinic anhydride N
1. , alkenylcova/acid Omo/ester and monoamide, 4-nonylphenoxyacetic acid.

b) Nitrogen-containing compounds, iFI: ■, aliphatic'! Or alicyclic first,! @Nika or tertiary amine b and amine salts of organic acids and inorganic acids, fll,
An oil-soluble alkyl ammonium carboxylate.

(2) Heterocyclic compounds, IFIJ, substituted iζ-dacillin D and oxazoline C) phosphorus-containing compounds 1-row dilinic acid anion salt or phosphonic acid monoester, zinc dialkyldithiophosphate.

d) Sulfur-containing compounds, such as barium dinonyl-naphthalene sulfonate, calcium petroleum sulfonate.

The list of viscosity index improvers is as follows. : Polyacrylate, polymethyl acrylate.

Vinylpyrrolidone/methacrylate copolymer Polyvinylpyrrolidone, polybutene, olefin copolymer, styrene/acrylate copolymer polyether.

Pour point depressant fIJFi, polymethacrylate.

It is an alkylated naphthalene derivative.

Examples of dispersants/surfactants are: : Polybutenyl succinimide tfch Polybutenyl succinimide, polybutenyl phosphonic acid derivatives, basic magnesium, calcium button and barium sulfonates and phenolates.

The anti-wear agents are as follows. : Compound 1 containing sulfur and/or phosphorus and/or halogen atom
For example, sulfurized vegetable oil, zinc dialkyldithiophosphate, tritolyl phosphate),! Paraffins, alkyl disulfides and aryl sulfides, alkyl trisulfides and aryl trisulfides, triphenyl phosphorothionate, jetanolaminomethyltolyltriazole, bis(2-ethylhexyl)aminomethyltolyltriazole.

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

(Example) The cyclic implementation fFl explains the invention in more detail.

Parts p and percentages represent parts by weight and percentages by weight*.

Example 1: The induction time of oxidation of an oil sample by No@400 PPm t-containing air was determined by differential scanning calorimeter (
Thermoanalyzer lQ90* DuPo
nt). Measurements were made at 170°C.
It was carried out under a pressure of bar. The pacing oil used was standard mineral oil (Aral 156), to which was added just over 1 volume of 1-decene to increase oxygen sensitivity. A ring amine stabilizer was added to the oil. : A-1: 2,2,4.4-tetramethyl-4-(3-methoxypropylamino)piperidine A-2: N, N'-
Bis(2,2,A, 6-tetramethylbiveridine-4
-yl) pentamethyldiamine A-3: N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine A-4: bis(2,2,6,A- Tetramethylpiperidin-4-yl)amine A-5: 2.2.6.6-tetramethyl-4-butylaminopiperidine.

Induction time t - given in Table 1. The longer the induction time, the
The antioxidant effect of the test stabilizer is great.

Table 1 Stabilizer Induction time (minutes) A-1α55% 72 A-2 (155% 132 A-3 (155%) 107 A-4 [155% 115 A-5 [155% 77 None 35 Patent applicant Civer-Geigy Akchen Gesell Shaft

Claims (9)

[Claims] (1) (A) Mineral oil, synthetic oil, or a mixture of these oils, and (B) Antioxidant stabilizer, formula I ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n represents 1 or 2. , R represents a hydrogen atom or a methyl group, R_1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, a benzyl group, -CO-R_4, -OR_5 or -O-CO-R_6
represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a hydroxyalkyl group having 2 to 5 carbon atoms, or formula II ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ represents a group represented by R_2, when n represents 1, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a hydroxy group having 2 to 5 carbon atoms; represents an alkyl group, an alkoxyalkyl group having 3 to 18 carbon atoms or a dialkylaminoalkyl group having 4 to 20 carbon atoms, and when n represents 2,
represents an alkylene group having 2 to 12 carbon atoms, a 2-hydroxy-1,3-propylene group or a xylylene group, R_4 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group, R_5 is a hydrogen atom , represents a C1-C12 alkyl group, a C5-C12 cycloalkyl group, or a benzyl group, and R_6 is a C1-C12 alkyl group, a C1-C12 alkoxy group, or Represents a phenyl group. ) A lubricant composition comprising a sterically hindered amine represented by the following formula, but containing no aromatic amine or phenolic antioxidant. (2) (B) represents the formula I (wherein n represents 1 or 2, R represents a hydrogen atom, R_1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group,
represents an acetyl group or -OR_5, R_2 represents a hydrogen atom, a C1-C4 alkyl group or a group represented by formula II, and R_3 represents when n represents 1;
represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, and when n represents 2, a group having 2 to 8 carbon atoms;
represents an alkylene group, and R_5 has 6 carbon atoms.
Represents 1 to 10 alkyl groups, cyclohexyl groups, or benzyl groups. ) Claim 1 is a compound represented by
Compositions as described. (3) (B) represents the formula I (where n represents 1 or 2, R represents a hydrogen atom, R_1 represents a hydrogen atom, methyl group or acetyl group, R_2 represents a hydrogen atom and R_3 represents a hydrogen atom, , when n represents 1, it represents a hydrogen atom or an alkoxyalkyl group having 3 to 8 carbon atoms, and when n represents 2, it represents 2 to 6 carbon atoms.
represents a cycloalkylene group. ) The composition according to claim 1, which is a compound represented by: 4. The composition according to claim 3, wherein (B) is a compound represented by formula I, where n represents 2 and R_2 represents an alkylene group having 2 to 6 carbon atoms. (5) The composition according to claim 4, wherein (B) is N,N'-bis(2,2,6,6-tetramethyl-pyridin-4-yl)hexamethylenediamine. (6) Based on (A), 0.1 to 2% by weight of (B)
The composition according to claim 1, comprising: (7) The composition according to claim 1, which is an engine oil. (8) comprising incorporating at least one compound represented by formula I according to claim 1, provided that aromatic amines and phenolic antioxidants are not added;
Methods for stabilizing lubricant compositions against oxidation-induced degradation. 9. The method of claim 8 for reducing sludge formation in engine oil, comprising incorporating at least one compound of formula I into the engine oil.