Lubricant composition containing multifunctional lubricant additives

The present invention provides a lubricant composition comprising a lubricating oil and, as a multifunctional additive, at least one compound of formula (I) ##STR1## in which R.sup.1 and R.sup.2 are, independently, hydrogen or C.sub.1 -C.sub.20 alkyl and R.sup.3 is hydrogen, C.sub.1 -C.sub.20 alkyl or a group of the formula ##STR2## wherein R.sup.4 is H or C.sub.1 -C.sub.20 alkyl. Most of the compounds of formula I are new.

This invention relates to new lubricant compositions containing 
multifunctional lubricant additives; to their use as multifunctional 
lubricant additives; to new compounds and to their production by reaction 
of 2,4,6-trimercapto-1,3,5-triazine (trithiocyanuric acid) with 
alpha-halogenated aliphatic carboxylic acids. 
The effective protection of metallic equipment from corrosion is a long 
standing problem. This problem is particularly acute in an environment in 
which ferrous metal comes into contact with a lubricant which may be 
contaminated with water, as in steam turbine oils. 
Another problem is presented by the friction generated between rubbing 
metal surfaces. This results in wear and occurs, for example, on the 
metallic parts in an apparatus such as a hydraulic pump. In addition, 
under conditions of high load, breakdown of the lubricant and seizure of 
metallic parts may occur. 
As an attempted solution to these problems, it is known that many lubricant 
additives will impart protection against one of corrosion, wear, extreme 
pressure or oxidation. However, additives which provide simultaneous 
protection against more than one of these phenomena are less common. 
In U.S. Pat. No. 2,836,564 there are disclosed new reaction products of 
alpha-halogenated aliphatic mono-carboxylic acids and 
2,5-dimercapto-1,3,4-thiadiazole and their use as rust inhibitors. In 
European Pat. No. 223,916 there are disclosed new reaction products of 
alpha-halogenated half esters or amides of succinic acid and thiazole 
dimercaptides and their use as multifunctional lubricant additives. 
The present invention provides a lubricant composition comprising a 
lubricating oil and, as a multifunctional additive, at least one compound 
of formula (I) 
##STR3## 
in which R.sup.1 and R.sup.2 are, independently, hydrogen or C.sub.1 
-C.sub.20 alkyl and R.sup.3 is hydrogen, C.sub.1 -C.sub.20 alkyl or a 
group of formula 
##STR4## 
wherein R.sup.4 is H or C.sub.1 -C.sub.20 alkyl. 
We have found certain new compounds, obtainable by reaction of 
2,4,6-trimercapto-1,3,5-triazine with alpha-halogenated aliphatic 
carboxylic acids which impart simultaneous superior rust inhibiting, 
anti-wear, extreme pressure and antioxidant properties when incorporated 
into a lubricant. 
The new compounds of the present invention have the formula (I): 
##STR5## 
in which R.sup.1 and R.sup.2 are, independently, H or C.sub.1 -C.sub.20 
alkyl and R.sup.3 is H, C.sub.1 -C.sub.20 alkyl or a group of the formula 
##STR6## 
wherein R.sup.4 is H or C.sub.1 -C.sub.20 alkyl with the proviso that when 
R.sup.3 is -CH.sub.2 CO.sub.2 H then R.sup.1 and R.sup.2 may not 
simultaneously be hydrogen. 
When R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are alkyl, the alkyl group may 
be straight or branched. 
Examples of C.sub.1 -C.sub.20 alkyl groups R.sup.1, R.sup.2, R.sup.3 and 
R.sup.4 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 
isooctyl, nonyl, decyl, undecyl, dodecyl, isododecyl, tridecyl, 
tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, 
isooctadecyl, eicosyl, isoeicosyl and isoamyl, 2-ethylbutyl, 
1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, 
1-methylhexyl, 1-methylheptyl, 1,1,3-trimethylhexyl and trimethylundecyl. 
Preferred compounds of formula (I) are those in which R.sup.1 and R.sup.2 
are C.sub.8 -C.sub.20 alkyl and R.sup.3 is C.sub.8 -C.sub.20 alkyl or 
R.sup.4 -CH-CO.sub.2 H in which R.sup.4 is C.sub.1 -C.sub.20 alkyl. 
Specific examples of compounds of formula I are indicated in the following 
Table. 
______________________________________ 
R.sup.1 R.sup.2 R.sub.3 
______________________________________ 
H H H 
H CH.sub.3 CH.sub.3 
H H CH.sub.3 
CH.sub.3 CH.sub.3 CH.sub.3 
C.sub.2 H.sub.5 
CH.sub.3 H 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
H 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
C.sub.10 H.sub.21 
C.sub.10 H.sub.21 
C.sub.10 H.sub.21 
C.sub.20 H.sub.41 
C.sub.20 H.sub.41 
C.sub.20 H.sub.41 
H CH.sub.3 --CH.sub.2 CO.sub.2 H 
CH.sub.3 CH.sub.3 --CH.sub.2 CO.sub.2 H 
H H --CH(CH.sub.3)CO.sub.2 H 
H CH.sub.3 --CH(CH.sub.3)CO.sub.2 H 
H H --CH(C.sub.18 H.sub.37)CO.sub.2 H 
______________________________________ 
The present invention also provides a process for the production of new 
compounds of the invention by reacting trithiocyanuric acid under alkaline 
conditions with 3 molar equivalents of an alpha-halogenated aliphatic 
carboxylic acid capable of introducing the groups 
##STR7## 
in which R.sup.1, R.sup.2 are, independently, hydrogen or C.sub.1 
-C.sub.20 alkyl and R.sup.4 is hydrogen or C.sub.1 -C.sub.20 alkyl; or 
with 2 molar equivalents of an alpha-halogenated aliphatic carboxylic acid 
capable of introducing the groups 
##STR8## 
and one molar equivalent of an alkyl halide of formula R.sup.3 -halide in 
which R3 is hydrogen, C.sub.1 -C.sub.20 alkyl or a group of formula 
##STR9## 
wherein R.sup.4 is hydrogen or C.sub.1 C.sub.20 alkyl. 
The reaction of 2,4,6-trimercapto-1,3,5-triazine under alkaline conditions 
with either 3 molar equivalents of an alpha-halogenated aliphatic 
carboxylic acid or 2 molar equivalents of an alpha-halogenated aliphatic 
carboxylic acid and one molar equivalent of an alkyl halide is illustrated 
e.g. by reaction schemes (1) and (2): 
##STR10## 
where R=R.sup.1 or R.sup.2 
M=NH.sub.4, Li, Na or K; 
X=Cl or Br; and 
HZ represents an inorganic acid e.g. HCl. 
The reaction scheme (1) may be carried out by treating, at below ambient 
temperature, 2,4,6-trimercapto-1,3,5-triazine with 6 molar equivalents of 
an alkali metal hydroxide dissolved in alcohol and subsequent addition of 
3 molar equivalents of an alpha-halogenated aliphatic carboxylic acid to 
the reaction mixture. The reaction mixture may then be allowed to warm to 
ambient temperature and may be then heated under reflux for a period of 
several hours. Ethyl alcohol is most suitable as reaction solvent but 
other solvents such as methanol, isopropanol and butanol may be used. Upon 
cooling, the reaction solvent may be removed, the residue acidified and 
the product isolated by solvent extraction. 
The reaction scheme (2) may be carried out in a similar manner with the 
exception that the 2,4,6-trimercapto-1,3,5-triazine may be treated 
initially with 4 molar equivalents of alkali and 2 molar equivalents of an 
alpha-halogenated aliphatic carboxylic acid. After a period of heating 
under reflux, the reaction mixture may be cooled and treated with a 
further molar equivalent of alkali and alkyl halide and then heated to 
reflux. The product may be isolated in the same manner as described in the 
scheme according to scheme (1). 
The compounds of formula (I) are active in imparting desirable properties 
to lubricants. They are particularly effective as corrosion inhibitors, 
antiwear and extreme pressure agents and also have some antioxidant 
properties. The said compounds are effective in amounts of e.g., 0.01-5 wt 
%, especially 0.02-1 wt % based on the lubricant. 
Preferred are lubricant compositions wherein the lubricating oil is a 
turbine oil or a hydraulic oil. 
The lubricating oil may be a mineral oil, a synthetic oil or any mixture of 
such oils. Mineral oils are preferred and examples of these include 
paraffinic hydrocarbon oils e.g. a mineral oil having a viscosity of 46 
mm.sup.2 /s at 40.degree. C.; "150 Solvent Neutral" a solvent refined 
neutral mineral oil having a viscosity of 32 mm.sup.2 /s at 40.degree. C.; 
and "Solvent brightstocks", a high boiling residue from the process of 
refining mineral oil, and having a viscosity of 46 mm.sup.2 /s at 
40.degree. C. 
Synthetic lubricating oils which may be present may be synthetic 
hydrocarbons such as polybutenes, alkyl benzenes and poly-alpha olefins as 
well as simple di-, tri- and tetra-esters, complex esters and polyesters 
derived from carboxylic acid esters of formula: 
EQU R.sup.5 --OOC--alkylene--COOR.sup.6 
wherein "alkylene" denotes an alkylene residue having from 2 to 14 carbon 
atoms and R.sup.5 and R.sup.6 are the same or different and each is an 
alkyl group having from 6 to 18 carbon atoms. Tri-esters which are of use 
as lubricating oil base stocks are those derived from trimethylolpropane 
and C.sub.6 -C.sub.18 mono-carboxylic acids or mixtures thereof, whereas 
suitable tetraesters include those derived from pentaerythritol and a 
C.sub.6 -C.sub.18 monocarboxylic acid or mixtures thereof. 
Complex esters suitable for use as components of the composition of the 
present invention are those derived from monobasic acids, dibasic acids 
and polyhydric alcohols, for instance the complex ester derived from 
trimethylol propane, caprylic acid and sebacic acid. 
Suitable polyesters are those derived from an alipahtic dicarboxylic acid 
having from 4 to 14 carbon atoms and at least one aliphatic dihydric 
alcohol having from 3 to 12 carbon atoms, e.g. those derived from azelaic 
acid or sebacic acid and 2,2,4-trimethylhexane-1,6-diol. 
Other lubricating oils are those known to the art-skilled and described 
e.g. in Schewe-Kobek, "Schmiermittel-Taschenbuch", (Huethig Verlag, 
Heidelberg 1974), and in D. Klamann, "Schmierstoffe und verwandte 
Produkte", (Verlag Chemie, Weinheim 1982). 
The lubricating oils applicational media can also contain other additives 
which may be added to improve the basic properties of lubricants e.g. 
metal passivators, viscosity-index improvers, pour-point depressants, 
dispersing agents, detergents, additional rust inhibitors, extreme 
pressure additives, anti-wear additives and antioxidants. 
EXAMPLES OF PHENOLIC ANTIOXIDANTS 
1. Alkylated Monophenols 
2,6-Di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 
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-i-butylphenol, 
2,6-di-cyclcopentyl-4-methylphenol, 
2-(.beta.-methylcyclohexyl)-4,6-dimethylphenol, 
2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 
2,6-di-tert-butyl-4methoxymethylphenol, o-tert-butylphenol. 
2. Alkylated Hydroquinones 
2,6-Di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 
2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol. 
3. Hydroxylated Thiodiphenylethers 
2,2'-Thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 
4,4'-thio-bis-(6-tert-butyl-3-methylphenol), 
4,4'-thio-bis(6-tert-butyl-2-methylphenol). 
4. Alkylidene-Bisphenols 
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-(.alpha.-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- or -5-isobutylphenol), 
2,2'-methylene-bis-(6-(.alpha.-methylbenzyl-4-nonylphenol), 
2,2'-methylene-bis-(6-(.alpha.,.alpha.-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-methylphenol)-butane, 
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl)-mercaptobu 
tane, 
ethyleneglycol-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'-methyl-benzyl)-6-tert-butyl-4-methyl-p 
henyl]-terephthalate. 
5. Benzyl Compounds 
1,3,5-Tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene, 
bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-sulfide, 
3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid-isooctylester, 
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate, 
1,3,5-tris-(3,5-di-tertbutyl-4-hydroxybenzyl)-isocyanurate, 
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 
3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-dioctadecylester, 
3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-monoethylester, 
calcium-salt. 
6. Acylaminophenols 
4-Hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 
2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, 
N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester. 
7. Esters of .beta.-(3,5-Di-tert-butyl-4-hydroxyphenol)-propionic acid with 
mono- or polyhydric alcohols, for example with methanol, diethyleneglycol, 
octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, 
neopentylglycol, tris-hydroxyethyl-isocyanurate, thiodiethyleneglycol, 
bis-hydroxyethyl-oxalic acid diamide. 
8. Esters of .beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid 
with mono- or polyhydric alcohols, for example with methanol, 
diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, 
pentaerythritol, neopentylglycol, tris-hydroxyethyl-isocyanurate, 
thiodiethyleneglycol, di-hydroxyethyl-oxalic acid diamide. 
9. Amides of .beta.-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionic acid for 
example 
N,N'-Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylene-diamine 
, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylene-diamin 
e, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine. 
Examples of amine antioxidants: 
N,N'-Di-isopropyl-p-phenylenediamine, 
N,N'-di-sec.-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phe 
nylenediamine, N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine, 
N,N'-bis(1-methyl-heptyl)-p-phenylenediamine, 
N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, 
N,N'-di-(naphthyl-2-)-p-phenylenediamine, 
N-isopropyl-N'-phenyl-p-phenylenediamine, 
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine, 
N-(1-methyl-heptyl)-N'-phenyl-p-phenylenediamine, 
N-cyclohexyl-N'-phenyl-p-phenylenediamine, 
4-(p-toluene-sulfonamido)-diphenylamine, 
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, 
N-allyldiphenylamine, 4-isopropoxy-diphenylamine, 
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated 
diphenylamine, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 
4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 
4-octadecanoylamino-phenol, di-(4-methoxy-phenyl)-amine, 
2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 
2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, 
N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane, 
1,2-di-(phenylamino)-ethane, 1,2-di-[2-methyl-phenyl)-amino]-ethane, 
1,3-di-(phenylamino)-propane, (o-tolyl)-biguanide, 
di-[4-(1',3'-dimethyl-butyl)phenyl]amine, tert-octylated 
N-phenyl-1-naphthylamine, mixture of mono-and dialkylated 
tert-butyl-/tert-octyldiphenylamines, 
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, 
n-allylphenothiazine. 
Examples for other antioxidants: 
Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of 
thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid. 
Examples of metal passivators, for example for copper, are: 
Triazoles, benzotriazoles and derivatives thereof, tolutriazole and 
derivatives thereof, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 
2,5-dimercaptothiadiazole, 2,5-dimercaptobenzotriazole, 
5,5'-methylene-bis-benzotriazole, 4,5,6,7-tetrahydrobenzotriazole, 
salicylidene-propylenediamine and salicylaminoguanidine and salts thereof, 
1,2,4-triazole and N,N-disubstituted aminomethyl triazoles of formula 
##STR11## 
in which R.sup.7 and R.sup.8 are, independently, e.g. alkyl, alkenyl, or 
hydroxyethyl, obtained by reacting 1,2,4-triazole with formaldehyde and an 
amine HNR.sup.7 R.sup.8, as disclosed in European Patent Application No. 
160620; and the Mannich reaction products derived from benzotriazole or 
tolutriazole, formaldehyde and an amine HNR.sup.7 R.sup.8. 
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 acids and -anhydrides, e.g. dodecenyl-succinic acid 
anhydride, succinic acid partial esters and amides, 4-nonyl-phenoxy-acetic 
acid. 
(b) Nitrogen-containing compounds, e.g. 
I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and 
amine-salts of organic and inorganic acids, e.g. oil-soluble alkylammonium 
carboxylates. 
II. Heterocyclic compounds, e.g. substituted imidazolines and oxazolines. 
(c) Phosphorus-containing compounds, e.g. 
amine salts of phosphonic acid or phosphoric acid partial esters, zinc 
dialkyldithio phosphates. 
(d) Sulfur-containing compounds, e.g. 
barium-dinonylnaphthalene-n-sulfonates, calcium petroleum sulfonates. 
(e) Derivatives of gamma- alkoxypropylamines described in Japanese Patent 
Publication No. 15783/1973; and 
(f) Salts having the formula Y--NH.sub.3 --R.sup.9 CO.sub.2.sup.- in which 
Y is a group R.sup.10 X.sub.1 CH.sub.2 CH(OH)CH.sub.2 in which R.sup.9 and 
R.sup.10 independently, are e.g. alkyl and X.sub.1 is O,CO.sub.2, NH, 
N(alkyl), N(alkenyl) or S, these salts being prepared by mixing an amine 
Y--NH.sub.2 with an acid R.sup.9 CO.sub.2 H, as disclosed in DE-OS 34 37 
876 (German Offenlegungsschrift). 
(g) Compounds having the formula 
EQU R.sup.a --X.sub.2 --CH.sub.2 --CH(OH)--CH.sub.2 NR.sup.b R.sup.c 
in which X.sub.2 is --O--, --S--, --SO.sub.2,--C(O)--O-- or --N(R.sup.d) in 
which R.sup.d is H or C.sub.1 -C.sub.12 alkyl, R.sup.b is unsubstituted 
C.sub.1 -C.sub.4 alkyl or C.sub.2 -C.sub.5 alkyl substituted by one to 
three hydroxyl groups, R.sup.c is hydrogen, unsubstituted C.sub.1 -C.sub.4 
alkyl or C.sub.2 -C.sub.5 alkyl substituted by one to three hydroxyl 
groups provided that at least one of R.sup.b and R.sup.c is 
hydroxy-substituted, and R.sup.a is C.sub.2 -C.sub.20 alkyl --CH.sub.2 
--CH(OH)--CH.sub.2 NR.sup.b R.sup.c or R.sup.a is C.sub.2 -C.sub.18 
alkenyl, C.sub.2 -C.sub.3 alkynyl or C.sub.5 -C.sub.12 cycloalkyl provided 
that, when X.sub.2 is --O-- or --C(O)--O--, R.sup.a is branched C.sub.4 
-C.sub.20 alkyl. These compounds are described in GB Patent Specification 
2172284A. 
(h) Compounds having the formula: 
##STR12## 
in which R.sup.e, R.sup.f, R.sup.g are, independently, hydrogen, C.sub.1 
-C.sub.15 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.6 -C.sub.15 aryl or 
C.sub.7 -C.sub.12 aralkyl and R.sup.h and R.sup.i, independently, are 
hydrogen, 2-hydroxyethyl or 2-hydroxypropyl, provided that R.sup.h and 
R.sup.i are not simultaneously hydrogen and, when R.sup.h and R.sup.i are 
each --CH.sub.2 CH.sub.2 OH, R.sup.e and R.sup.f are not simultaneously 
hydrogen and R.sup.g is not pentyl. These compounds are described in EP 
Patent Specification 0 252 007. 
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: 
Polymethacrylates, alkylated naphthalene derivatives. 
Examples of dispersants/detergents are: 
Polybutenylsuccinic acid-amides or -imides, polybutenylphosphonic acid 
derivatives, basic magnesium-, calcium-, and bariumsulfonates and 
-phenolates. 
Examples of anti-wear additives and extreme pressure additives are: 
Sulfur- and/or phosphorus- and/or halogen-containing compounds e.g. 
sulfurised vegetable oils, zinc dialkyldithiophosphates, 
tritolylphosphate, chlorinated paraffins, alkyl- and aryldi- and 
trisulfides, triphenylphosphorothionate, diethanolaminomethyltolutriazole, 
di(2-ethylhexyl)-aminomethyltolutriazole. 
The present invention also includes a process of improving the rust 
inhibiting, antiwear, extreme pressure and antioxidant properties of 
lubricating oils by incorporation of at least one compound of formula I, 
as mentioned above, into said lubricant. 
Further, the present invention includes the use of at least one compound of 
formula I, as mentioned above, in a lubricating oil in order to improve 
the rust inhibiting, antiwear, extreme pressure and antioxidant properties 
thereof.

The following examples further illustrate the invention: 
In these examples, all parts and percentages given are by weight unless 
otherwise specified. 
Example 1 Preparation of 2,2', 
2"-[1,3,5-triazine-2,4,6-triyltris-(thio)]tris dodecanoic acid 
A stirred solution of KOH (12.8 g; 0.228 mole) in ethanol (350 ml) is 
cooled to 10.degree. C. and treated with trithiocyanuric acid (6.8 g; 
0.038 mole). After stirring for 30 minutes, the reaction mixture is 
treated with 2-bromododecanoic acid (31.8 g; 0.114 mole) in small portions 
over 10-15 minutes. The resulting thick, white suspension is stirred for a 
further 30 minutes at 10.degree. C. and is then allowed to warm to ambient 
temperature. Upon reaching ambient temperature the reaction mixture is 
heated to reflux and maintained at this temperature for 6 hours. 
The reaction mixture is cooled to ambient temperature and the solvent is 
removed under reduced pressure. The white, waxy residue is suspended in 
water (150 ml) and acidified with concentrated HCl to pH 1. The acidified 
aqueous suspension is then extracted with ether (200 ml) and the ether 
extract is washed with water (2.times.80 ml). The extract is dried over 
MgSO.sub.4, filtered, then evaporated to yield 25.9 g (88 %) of a yellow 
waxy solid product. 
Analysis Found: C 60.65 %; H 9.19 %; N 5.67 %. 
C.sub.39 H.sub.69 N.sub.3 O.sub.6 S.sub.3 requires: C 60.66 %; H 9.01 %; N 
5.44 %. 
Example 2 Preparation of 2,2', 
2"-[1,3,5-triazine-2,4,6-triyltris-(thio)]tris octadecanoic acid. 
The procedure of Example 1 is repeated but substituting 2-bromooctadecanoic 
acid for 2-bromododecanoic acid. The product is a yellow solid, mp 
37.degree. C., obained in 68 % yield. 
Analysis Found: C 65.76 %; H 10.39 %; N 3.97 %. 
C.sub.57 H.sub.105 N.sub.3 O.sub.6 S.sub.3 requires: C 66.81 %; H 10.33 %; 
N 4.10 %. 
Example 3 Preparation of 
2,2'-[2-dodecylthio-1,3,5-triazine-4,6-diylbis-(thio)]bis dodecanoic acid. 
A stirred solution of KOH (5.6 g; 0.1 mole) in ethanol (100 ml) is cooled 
to 5-10.degree. C. and treated with trithiocyanuric acid (4.42 g; 0.025 
mole). After stirring for 30 minutes, the reaction mixture is treated with 
2-bromododecanoic acid (13.9 g; 0.05 mole) in small portions over 10-15 
minutes. The resulting white suspension is stirred for a further 30 
minutes at 10.degree. C. and is then allowed to warm to ambient 
temperature. Upon reaching ambient temperature, the reaction mixture is 
heated to reflux and maintained at this temperature for 3 hours. The 
reaction mixture is then cooled to 5.degree. C. and treated with a 
solution of KOH (1.4 g; 0.025 mole) in ethanol (50 ml) followed by dodecyl 
bromide (6.2 g; 0.025 mole). The reaction mixture is allowed to warm to 
ambient temperature and is then heated to reflux and maintained at this 
temperature for 2 hours. The reaction mixture is cooled to ambient 
temperature and the solvent removed under reduced pressure. The residue is 
suspended in water (100 ml and acidified with concentrated HCl to pH 3. 
The acidified aqueous suspension is then extracted with either (200 ml) 
and the ether extract is washed with water (3.times.50 ml). The extract is 
dried over MgSO.sub.4, filtered, then evaporated to yield 14.7 g (79 %) of 
a yellow viscous oil. 
Analysis Found: C 63.22 %; H 9.80 %; N 5.32 %. 
C.sub.39 H.sub.71 N.sub.3 O.sub.4 S.sub.3 requires: C 63.11 %; H 9.64 %; N 
5.66 %. 
Examples 4 to 9 
The rust inhibiting, antiwear, extreme pressure and anti-oxidant properties 
of the compounds of the invention are determined by the following methods: 
TABLE 1 
______________________________________ 
Rust inhibition - ASTM D-665 (IP 135) Test 
______________________________________ 
The method involves stirring a mixture of 300 ml of the 
oil under test with 30 ml of synthetic sea water, at a temperature 
of 60.degree. C. (140.degree. F.) with a cylindrical steel specimen 
completely 
immersed therein. It is customary to run the test for 24 h. 
This method of test is intended to indicate the ability of 
stream-turbine oils and heavier-than-water fluids, including those 
used for stream-turbine gears, to aid in preventing the rusting 
of ferreous parts should water become mixed with the oil. 
Measured is the degree of corrosion of the steel specimen. 
______________________________________ 
Example Test Oil Test result 
______________________________________ 
-- Base Oil.sup.1 (Control) 
severe rust after 24 hrs 
4 Base Oil containing 
no rust after 24 hrs 
0.05% by weight 
product of Example 1 
5 Base Oil containing 
no rust after 24 hrs 
0.05% by weight 
product of Example 2 
6 Base Oil containing 
no rust after 24 hrs 
0.05% by weight 
product of Example 3 
______________________________________ 
TABLE 2 
______________________________________ 
Extreme Pressure and Antiwear Properties ASTM D 2783-81 
(IP 239/79) Test 
______________________________________ 
The method using the Shell four-ball apparatus is 
employed to test for suitability for anti-wear 
protection. The following are determined: 
(a) the weld load WL, as the load (in kg) at which 
the 4 balls weld together in the course of 10 seconds, 
and (b) the average wear scar diameter WSD at a 
load of 40 kg for 1 hour (in mm). 
______________________________________ 
Test result 
Wear Scar Weld Load 
Example 
Test Oil Diameter (mm) 
[kg] 
______________________________________ 
-- Base Oil.sup.1 1.00 125 
7 Base Oil containing 
0.60 145 
0.05% by weight 
product of Example 1 
8 Base Oil containing 
0.54 140 
0.05% by weight 
product of Example 3 
______________________________________ 
TABLE 3 
______________________________________ 
Antioxidant Properties (ASTM D 2272 (IP 229) Test) 
______________________________________ 
The oil oxidation test, Rotary Bomb Oxidation Test, 
is carried out in the following way. An oil sample of 
50 ml is oxidised in an oxygen atmosphere, in a 
glass vessel, together with 5 ml of distilled water 
and a polished, catalytically active Cu spiral 
washed with petroleum ether. 
The glass vessel is in a stainless steel bomb with 
a manometer. The bomb rotates axially at 100 rpm, at an 
angle of 30.degree. to the horizontal, in an oil bath at 
150.degree. C. The oxygen pressure is initially about 620 kPA 
(90 psi), before heating, increases to exactly 1400 kPA 
at 150.degree. C. and remains constant until oxidation has started. 
The test has ended when there has been a pressure drop of 
175 kPa (25,4 psi). The time is recorded in minutes. 
Long time values correspond to a high degree in 
stabilizer effectiveness. 
______________________________________ 
Example Test Oil Bomb life 
______________________________________ 
-- Base Oil.sup.1 25 minutes 
9 Base Oil containing 
68 minutes 
0.25% by weight 
product of Example 1 
______________________________________ 
.sup.1 Turbine grade mineral oil of viscosity 31.6 mm.sup.2 /s at 
40.degree. C., 4.6 mm.sup.2 /s at 100.degree. C. and a sulphur content of 
0.6%.