CA1340293C

CA1340293C - Additives for functional fluids

Info

Publication number: CA1340293C
Application number: CA000602279A
Authority: CA
Inventors: Hermann O. Wirth; Hans-Helmut Friedrich; Klaus Muller
Original assignee: Ciba Spezialitaetenchemie Holding AG
Current assignee: BASF Schweiz AG
Priority date: 1988-06-13
Filing date: 1989-06-09
Publication date: 1998-12-29
Anticipated expiration: 2015-12-29
Also published as: ES2062090T3; DE58906927D1; EP0349483A3; EP0349483B1; JP2791495B2; KR910001009A; AU3630389A; AU621123B2; BR8902776A; JPH0232052A; EP0349483A2

Abstract

Compounds of the formula (see fig. I) in which R1 and R2 are identical or different and are tert-C4 to tert-C7alkyl, C5 to C10cycloalkyl or pinane-10-yl, and Q is -S-, -S-S-, -S-CH2-S- or -S-CH2-CH2-S-, and compositions which comprise a functional fluid of the series of lubricants, hydraulic fluids or metalworking fluids and at least one compound of the formula I. The compositions may be employed especially in the lubrication system of diesel and spark-ignition engines and they reduce especially the wear on the cams of the camshafts and on the tappets of the valve train.

Description

o293 Additives for functional fluids The present invention relates to novel compounds containing thioether groups, to functional fluids of the series of lubricants, such as lubricating oils and greases, hydraulic fluids and metalworking fluids comprising compounds containing thioether groups, and to the use of these compounds as additives.

Various additives are generally added to functional fluids to improve their performance properties. Since, for example, lubricating oils must possess a high load-bearing capacity for the transference of more powerful forces, they are treated by the so-called extreme-pressure and antiwear additives, which treatment markedly reduces the wear phenomena which would otherwise occur. On the other hand, when oxygen and moisture, for example, jointly act on a metal surface, corrosion may take place, for which reason corrosion inhibitors are added. The oxidation reactions, for example, which occur under the action of atmospheric oxygen and do so to a much greater degree at elevated temperatures, can be inhibited by the addition of antioxidants. It is known that some substances used as additives for lubricating oils can combine several such characteristics;
they are referred to as multipurpose additives. Such substances are naturally much sought after on economic and practical grounds.

US-PS 4,246,127, for example, discloses disulfides and polysulfides andtheir use as lubricant additives. EP-A 0,166,696 furthermore discloses compounds containing thioether groups and compositions thereof with lubricants and hydraulic fluids.

- 2 - 1 3 ~ 0293 Compound~ containing thioether groups have now been found which in compositions with lubricants, hydraulic fluids or metalworking fluids possess quite outstanding properties and which in combination, for example, with lubricating oils distinctly enhance the performance of the latter compared with compounds described earlier.

The present invention relates to compounds of the formula R1-5-CHz-ÇH-CHz-Q-CH2-CIH-CH2-s-R2 (I) in which R1 and R2 are identical or different and are tert-C4 to tert-C7alkyl or C5 or C6cycloalkyl, and Q is -S~ S-S-, --S-CH2-S- or -S-CH2--CH2--S--.

The compounds are expediently of the formula I, where R1 and R2 are identical. In the formula I, R1 and R2 are preferably tert-butyl or cyclohexyl.

Particularly preferred compounds are tert.-Butyl-S-CHz-Ç}1-CH2-S-CH2-~H-CHz-S-tert.-Butyl (III), H H

tert.-Butyl-S-CHz-ÇH-CHz-5-S-CHz-~H-CHz-S-tert.-Butyl (IV), H H

tert.-Butyl-S-CHz-CI~-CH2-S-CI12-S-CI12-C~-CI12-S-tert.-Butyl (V), 0~ 0 tert.-Butyl-S-CHz-ÇH-CH2-S-CH2-C112-S-CH2-ÇH-CH2-S-tert.-Butyl (VI), OH OH

S-CHz~ÇH~CH2~S-CHz~ÇH~CH2-S~-/ \- (VII), ._. ._.
~\ /--S-Cli2-~CH-CI12-S-S-CH2-ÇII-C112-S--~ /- (VIII), ~\ /--s-cH2-çH-cH2-s-cl~2-s-cl~2-~l~-cl~2-s--\ /- (IX), ~ 3 ~ 1 ~ 40 293 ~ . . .
~/ \~--S--CH2--8H--CH2--S--CH2--CH2--S--CH2--8H--CH2--S--~/\. (X), CH2-s-cH2-cH-cH2-s-cH2-8H-cH2-s-cH2 H3C\i\ i i /i~CH3 (XI), H3C/ '!' '!' \CH

CH2-S-CHz-8H-CH2-S-S-CH2-8H-CH2-S-CH2 H3C\i\ i i /i~CH3 (XII), H3C/ '!' '!' \CH

/CHz-S-CH2-8H-CH2-S-CH2-S-CH2-8H-CH2-S-CH2\
H3C\i\ i ~/ \i/CH3 (XIII) H3C ~ \1/ CH3 and CH2-S-CHz-CH-CH2-S-CH2-CH2-S-CH2-8H-CH2-S-CH2 H3C\i\ i i /i~CH3 (XIV).
H3C ~/ \1/ \CH

The present invention also relates to compositions which comprise a) a functional fluid of the series of lubricants, hydraulic fluids and metalworking fluids, and b) at least one compound of the formula Rl-S-CHz-8H-CH2-Q-CH2-8H-CH2-S-R2 (I) H H
in which Rl and R2 are identical or different and are C3 to C7alkyl, Cs to Clocycloalkyl or pinane-10-yl, and Q is -S-, -S-S-, -S-CHz-S- or -S-CHz-CH2-S-.

1~4~293 The present invention relates especially to compositions which comprise a) a lubricating oil of the series of mineral oils, synthetic oils or mixtures thereof, and b) at least one compound of the formula I.

The compositions expediently comprise at least one compound of the formula I, in which Rl and R2 are tert-C4 to tert-C7alkyl or Cs or C6cycloalkyl. These compositions expediently comprise at least one compound of the formula I in which Rl and R2 are identical.

The compositions preferably comprise at least one compound of the formula I in which Rl and R2 are both tert-butyl or cyclohexyl.

Compositions which are particularly preferred comprise at least one of the compounds of the formulae tert.-Butyl-s-cH2-8H-cH2-s-cH2-8H-cH2-s-tert--Butyl (III), H H

tert.-Butyl-s-cH2-8H-cH2-s-s-cH2-8H-cH2-s-tert--Butyl (IV), H H

tert.-Butyl-S-CHz-C~-CH2-S-CH2-S-CH2-C~-CH2-S-tert.-Butyl (V), O O

tert-~BUtYl~S~CH2~8H~CH2-S-CH2-CH2-S-CH2-8H-CH2-S-tert.-Butyl (VI), H H

\ _ / S CHz 8H CH2-S-CH2-8H-CH2-S--~ \- (VII), .\ /.-s-cH2-8H-cH2-s-s-cH2-8H-cH2-s-.\ /. (VIII), ~-- H H ~--~/ \--s-cH2-8H-cH2-s-cH2-s CHz 8H CH2 S \ _ / (IX), ~/ \~--S--CH2--8H--CH2--S--CH2--CH2--S--CH2--8H--CH2--S--~/ \~ (X), - 5 ~ 1340293 /CHz-S-CH2-8H-CH2-S-CH2-8H-CH2-S-CH2\
H3C\i\ i i /i~CH3 (XI), H3C ~ ~ CH3 /CH2-S-CH2-8H-CH2-S-S-CH2-8H-CH2-S-CH2\
H3C\i\ i i /i~CH3 (XII), H3C \-/ \1/ \CH3 /CHz-S-CH2-~H-CH2-S-CH2-S-CH2-8H-CH2-S-CH2~
H3C\i\ i i /i~CH3 (XIII) H3C ~ ~ CH3 or /CH2-S-CH2-8H-CH2-S-CH2-CH2-S-CH2-8H-CH2-S-CH2\
H3C\i\ i i /i~CH3 (XIV).
H3C ~ ~ CH3 Rl and R2 in the formula I independently of one another are an alkyl group having 3 to 7 carbon atoms and can be, for example, a tert-butyl or a pentyl, hexyl or heptyl group, it being possible also for the last three groups to contain a tertiary substituted carbon atom.

Rl and R2 in the formula I independently of one another are a cycloalkyl group having 5 to 10 carbon atoms and can be, for example, a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl group.
Preferred is a cyclohexyl group. Rl and R2 in the formula I independently of one another are for example pinane-10-yl having the formula !cH2-H 3 C~ i / \i The preparation of the compounds according to the present invention is carried out in a manner known per se.

~340293 The preparation of the alkyl thiaglycidyl ethers employed as intermediate for the compounds of the formula I, is performed in the following manner:

R-SH + Cl-CH2-C~ /CHz -NaCl/-H 0 R-S-CH2-C~--/CHz (II), in which the substituent R is as defined above for R1 or R2. The use of a phase transfer catalyst, for example tetrabutylammonium chloride, is particularly advantageous for this reaction. The preparation of alkyl thiaglycidyl ether is also described in US-A-2,965,652, US-A-2,731,437 and BE-A-609,375.

The alkyl thiaglycidyl ethers of the formula II may then be reacted, for example, with sodium hydrogen sulfide to form compounds of the type of the formula III, VII or XI. The mercaptans which are formed by the addition of H2S to compounds of the formula II, may be converted to compounds of the type of the formula IV, VIII or XII using, for example, dimethylsulfoxide. These mercaptans furnish with formaldehyde compounds of the type of the formula V, IX or XIII while the addition of compounds of the type of the formula II to 1,2-dimercaptoethane gives rise to compounds of the type of the formula VI, X or XIV.

The compounds of the formula I function already in very low amounts as additives in functional fluids, such as lubricating oils, hydraulic fluids and metalworking fluids. They are expediently added to the functional fluids in an amount of 0.01 to 5 % by weight, preferably in an amount of 0.05 to 3 % by weight, based on the functional fluid.

The lubricating oils in question are familiar to the person skilled in the art and are described, for example, in "Schmierstoffe und verwandte Produkte" ["Lubricants and Related Products"] by Dieter Klamann, (Verlag Chemie, Weinheim, 1982) or in "Das Schmiermittel-Taschenbuch" ["Lubri-cants Handbook"] by Schewe-Kobek, (Dr. Alfred Huthig-Verlag, Heidelberg, 1974). In addition to mineral oils, poly-~-olefins, ester-based lubri-cants, phosphates, glycols, polyglycols and polyalkylene glycols, are particularly suitable.

- 7 ~ 0 2 9 3 The compounds of the formula I are readily soluble in lubricants, are accordingly particularly suitable as additives, for example, to lubri-cating oils and greases and enhance the extreme-pressure and antiwear properties. The oxidation-preventive and corrosion-preventive action of these compounds even toward copper should be also pointed out. Further-more, common sealant materials are not attacked. Finally and surprising-ly, the preparation of so-called masterbatches is possible.

The presence of compounds of the formula I in lubricants allows at least a partial replacement of ash-producing additives, i.e. especially zinc compounds or phosphorus-containing additives, principally zinc dithio-phosphates. It is desirable to limit the amounts of zinc and its com-pounds and especially of phosphorus and its compounds, or avoid their use altogether, as a component of an additive for a gasoline engine motor oil in view of the possibility that the catalyst attached nowadays to the exhaust of a gasoline engine may be deactivated by the zinc and phos-phorus compounds discharged in the exhaust gases.

In contrast to the possible impairment of the catalyst of a gasoline engine by the additives used hitherto, the compounds of the formula I
according to the present invention allow a continued reduction in phosphorus and thereby enhance the operational reliability of the catalyst.

Novel compounds and novel functional fluid compositions and especially lubricating oil compositions containing these compounds having properties further improved compared with products known hitherto, have also been found. The products are distinguished by high resistance to oxidative degradation and to solvolytic cleavability, and they impart, for example, to lubricating oil compositions a surprisingly high wear resistance which is particularly effective on the valve train, i.e. on the cams of the camshafts and on the tappets of diesel engines and spark-ignition engines. Furthermore, the compounds of the formula I and the compositions comprising these compounds have a good seal compatibility and they do not corrode copper.

- ~340293 The compositions according to the invention are suitable for use as lubricating oil compositions for internal combustion engines in general, they are particularly suitable for diesel engines and are very parti-cularly suitable for spark-ignition engines. The term "spark-ignition engines" refers to internal combustion engines operating on the piston stroke principle. Internal combustion engines may be used for a variety of purposes, for example in stationary engines or as drives in means of transport such as ships, aircraft and especially in motor vehicles.

The invention can relate to compositions, for example, in which the lubricating oil is an oil for diesel engines or spark-ignition engines.

The present invention accordingly also relates to the use of compounds of the formula I as multipurpose additives for lubricants, hydraulic fluids and metalworking fluids. Compounds of the formula I are expediently employed in lubricating oils as multipurpose additives. Compounds of the formula I are preferably used as extreme-pressure and antiwear additives in lubricants and especially in lubricating oils.

The compositions according to the invention also relate expediently to low-ash or ashless and phosphorus-free compositions which comprise (a) a mineral oil or a synthetic oil or a mixture thereof or a hydraulic fluid or a metalworking fluid, and (b) at least one compound of the formula (I).

The present invention accordingly also relates to the use of compounds of the formula I as phosphorus-free extreme-pressure and antiwear additives for lubricants, hydraulic fluids or metalworking fluids.

The invention refers particularly to compositions of the specified type according to API classification SF, SG, CD and/or CE or according to CCMC
categories G 1, G 2, G 3, D 1, D 2, D 3 and/or PD 1.

Accordingly, the compositions expediently represent motor oils for motor vehicles, and essentially for passenger car engines and light commercial vehicle engines, which correspond to at least one of the categories SF, SG, CD or CE of the API (American Petroleum Institute) classification and . ~

9 1340~93 to at least one of the categories G 1, G 2, G 3, D 1, D 2, D 3 or PD 1 of the CCMC (Committee of Common Market Automobile Constructors) classifi-cation.

The invention also comprises a method for reducing wear in diesel engines and spark-ignition engines, and in particular on the cams of the cams-hafts and on the tappets of the valve train, wherein the lubricating system of the internal combustion engine is run on a composition of the type described above.

The invention also comprises a method for avoiding the deactivation of the catalyst attached to the exhaust of a gasoline engine, wherein the lubricating system of the internal combustion engine is run on a compo-sition of the type described above.

The lubricants may additionally contain other additives, added for the purpose of further improving the basic properties of the lubricants;
these include: antioxidants, metal passivators, corrosion inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents as well as further extreme-pressure additives and antiwear additives. The above reservations concerning ash-producing compounds, especially zinc compounds, and phosphorus compounds are accordingly also valid for the additional additives, a certain content of zinc-containing phosphorus/sulfur compounds being tolerated.

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-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(~-methylcyclohexyl)-4,6-dimethylphenol, 2,6-diocta-decyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol.

134~293 2. Alkylated hydroquinones 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

3. Hydroxylated thiodiphenyl ethers 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-(~-methyl-cyclohexyl)phenol], 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2'-methylene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(6-tert-butyl-4- or -5-iso-butylphenol), 2,2'-methylene-bis[6-(~-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(~,~-di-methylbenzyl)-4-nonylphenol], 4,4'-methylene-bis(2,6-di-tert-butyl-phenol), 4,4'-methylene-bis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)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-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]tere-phthalate.

5. Benzyl compounds 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl)isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

6. Acylaminophenols 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

7. Esters of B-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, trishydroxyethyl isocyanurate, thiodiethylene glycol, bishydroxyethyloxaldiamide.

8. Esters of B-( 5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, trishydroxyethyl isocyanurate, thiodiethylene glycol, dihydroxyethyloxaldiamide.

9. Amides of B-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid for example N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpro-pionyl)hydrazine.

Examples of aminic antioxidants:
N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenedi-amine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphthyl-2)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfonamido)di-phenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, di-phenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyryl-aminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octa-- 12 - ~ 3~ 0293 decanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-di-methylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodi-phenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-l-naphthylamine, mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine.

Examples of other antioxidants:
aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid.

Examples of metal deactivators, for example for copper:
triazoles, benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2,5-di-mercaptobenzotriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylenebis-benzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidenepropylenedi-amine, salicylaminoguanidine and their salts.

Examples of rust inhibitors:
a) Organic acids, their esters, metal salts and anhydrides, for example:
N-oleoylsarcosine, sorbitol monooleate, lead naphthenate, alkenylsuccinic anhydride, for example dodecenylsuccinic anhydride, alkenylsuccinic hemiester and hemiamide, 4-nonylphenoxyacetic acid.

b) Compounds containing nitrogen, for example:
I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates.

II. Heterocyclic compounds, for example:
substituted imidazolines and oxazolines.

c) Compounds containing phosphorus, for example:
amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates.

- 13 - 13~0293 d) Compounds containing sulfur, for example:
barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.

Examples of viscosity index improvers:
polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copoly-mers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/
acrylate copolymer, polyethers.

Examples of pour point depressants:
polymethacrylate, alkylated naphthalene derivatives.

Examples of dispersants/surfactants:
polybutenylsuccinamide or polybutenylsuccinimide, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of antiwear additives:
compounds containing sulfur and/or phosphorus and/or halogens, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides, alkyl and aryl trisulfides, triphenylphosphorothionates, diethanolaminomethyltolyl-triazole, di(2-ethylhexyl)aminomethyltolyltriazole.

The examples below elucidate the invention in greater detail. The partsand percentages are parts and percentages by weight, unless stated otherwise.

Example 1: preparation of tC4Hg-S-CHz-8H-CHz-S-CHz-8H-CHz-S- C4Hg tIII) H H

~ 340293 Reactlon scheme 2tC~Hg-s-CH2~ ~ ~ CH2 + NaSH(~ % ~ H2O) + H~O

~

~ ~C ~ ~ H4--S--CH2--CH--CH2--)2S ~NaOH

OH

73.1 g (0.5 mol) of tert-butyl glycldyl thloether are added dropwlse wlth stlrrlng to 50 ml (0.268 mol) of technlcal 30 sodlum hydrogen sulflde solutlon, contalned ln a four-necked flask and dlluted wlth 25 ml of water (duratlon about 1 hour).
The temperature of the reactlon mlxture whlch heats up ln the reactlon, ls kept to 40-50~C by coollng. Stlrrlng ls then contlnued at 50-60~C for 1 hour and the endpolnt of the reactlon ls checked by the dlsappearance of the glycldyl thloether spot ln the thln-layer chromatogram.

Worklng up ls carrled out vla phase separatlon.

The organlc phase ls the reactlon product. It ls washed wlth about 20 ml of dllute sodlum blcarbonate solutlon and ls flltered, after clear phase separatlon, through CELITE
and ls drled.

Trade-mark i, ~

~ 3~029~
- 14a -Yleld: 77.6 g~g5 % of theory; yellow vlscous llquld;
refractlve lndex n2~D:1.5261; bolllng polnt: 180~C/0.5 mbar Example 2: preparatlon of Herstellung von OH

~ ~ Hg- S - CH2 - CH - CH2 - )2 Vl Reactlon scheme 2~C4Hg - S-GH2- @ - CH2+ HS - CH2 - CH2 - SH CH~, OH
~ ~ Hg- S - CH2 - CH - CH2 - S- CH2 -)2 Procedure 1=8.8 g (0.2 mol) of 1,2-dlmercaptoethane and 0.5 ml of sodlum methylate solutlon (30 % ln methanol), contalned ln a two-necked flask, are warmed to 60~C, the heatlng bath ls removed and 61.4 g (0.42 mol) of tert-butyl glycldyl thloether are added dropwlse ln the course of ~ ~ 10293 45 minutes at 60-70~C with stirring (exothermic reaction). When the addition is completed, the mixture is further stirred for 30 minutes at about 60~C and volatile substances are removed in vacuo in a rotary evaporator. Working up is carried out as in Example 1.

Yield: 100 % of theory; colourless liquid; refractive index: n2D: 1. 5391 Example 3: preparation of ( C4Hg-S-CH2- H-CH2-S--)2 IV

Reaction scheme:

2 C4Hs-S-CH2- H-CH2-SH + (CH3)2S = 0 -HzO ~ (tc4Hg-s-cH2-cH-cH2-s-)2 QH
36 g (0. 5 mol) of the compound tert-C4Hg-S-CH2-CH-CH2-SH, 31.2 g (0.4 mol) of dimethyl sulfoxide and 150 ml of toluene are combined in a reaction vessel and 1.7 ml of the water of reaction is removed with stirring by reflux. About 100 ml of toluene/dimethyl sulfoxide are then distilled off at normal pressure, the organic phase is treated with 50 ml of toluene, washed with aqueous sodium bicarbonate solution and then with water, dried and concentrated.

Yield: 34.7 g~~6.7 % of theory, yellow liquid; refractive index n2 D: 1.5450 Example 4:
Wear test:
Each of the compounds III, IV and VI, prepared as in Examples 1 to 3, is mixed with an SAE 10 W-30 motor oil free from zinc dithiophosphates (the base oil being an IS0 VG 32 mineral oil), designated AARG 45, at a concentration of 1 % by weight, and the samples are subjected to the so-called cam and tappet (C + T) test.

. . .
~ 5~=

- 16- ~-340~9 Brief description of the C + T test:
In an enclosed housing, a cam made of cast iron induction-hardened to 550-580 HV (Vickers hardness) rotates against a spring-loaded tappet made of casehardened steel of 800-850 HV hardness. The housing is filled with the test oil up to the middle of the cam axle. The oil is heated to 100~C
by means of built-in heating rods. When the required temperature is reached, the force acting on the cam head is set to 1,000 N by adjusting the spring pressure and the test is commenced at a speed of rotation of the cam of 1,500 rpm. The wear is measured after one hour's running. If the total wear of cam head and tappet is less than 0.25 mm, the force acting on the cam head is increased by 100 N and the test is continued for a further hour at the increased cam force until either the wear is greater than 0.25 mm or a cam head force of 2,000 N is reached.

The result is reported as damage stage or, in the absence of any wear, is recorded as greater than 2,000.

Table 1 lists the measured values, a higher numerical value (in N) representing an improved antiwear performance.

Table 1 Base oil AARG 45 1000 + 1 % compound of the formula III (Example 1) 1700 + 1 % compound of the formula IV (Example 2) 1800 + 1 % compound of the formula VI (Example 3) 1900 Example 5:
Oxidation stability test The compounds prepared in Examples 1 and 2 (additives III and VI) are subjected to the TFOU test.

- 17 - ~ ~40293 (TFOU test Thln-Fllm Oxygen Uptake Test, Natlonal Bureau of Standards (NBS), Washlngton DC, USA) Thls test ls a modlfled version of the "Rotary Bomb Oxldatlon Test for Mlneral Olls" (RBOT) (ASTM D 2272). It ls descrlbed ln full ln the paper by C.S. Ku and S.M. Hsu, A
Thln-Fllm Oxygen Uptake Test for the Evaluatlon of Automotlve Crankcase Lubrlcants, Lubrlcatlon Englneerlnq, Vol. 40 (2), 75-83 (1984). In the TFOU test, the oll under test (1.5 g), contalned ln a glass tube placed lnslde a steel pressure contalner (bomb), ln the presence of 2 % of water, a llquld oxldlzed and nltrated fractlon of a motor gasollne as catalyst (4 % lnltlal concentratlon) and a llquld metal naphthenate as a further catalyst (4 % lnltlal concentratlon) (the water and the two llquld catalysts are avallable from the Natlonal Bureau of Standards (NBS) under the Standard Reference Materlal No. 1817 wlth certlflcate of analysls), ls sub~ected to oxygen pressure of 6.3 bar (90 psl) (oxygen volume 65 ml).
The bomb rotates ln a sloplng posltlon at 100 rpm ln a llquld bath at 160~C. The sloplng posltlon and the rotary movement cause the oll to be dlstrlbuted as a fllm on the surface of the glass contalner.
After a glven lnductlon tlme, the oll beglns to oxldlze under these condltlons. The oxldatlon lnduces oxygen uptake, manlfested by a dlstlnct pressure drop. The perlod to the onset of oxldatlon, the so-called lnductlon tlme, ls taken as a measure of oxldatlon stablllty.

", . , . , ,,, ~, , ~ 340293 - 17a -The test oll used is a motor oll based on an ISO VG
32 mlneral oll, comprlslng an addltlve package Oloa 4140 C
(Orogll) and a vlscoslty lndex lmprover (an olefln copolymer).
The vlscoslty corresponds to 15W-50 and the zlnc dlthlophosphate content of the addltlve glves rlse to an analytlcal value of 0.067 % of Zn and 0.06 % of P ln the oll.
The results glven ln Table 2 below represent the tlme (ln mlnutes) to the break ln the pressure/tlme dlagram.
Long perlods correspond to effectlve stablllzlng actlon. Concentratlon of the addltlves III and VI: 0.75 % by welght based on the oll.

Trade-mark r ,; ~

- 18 - ~ 3~0293 Table 2 TFOUT min Base oil 68 + 0,75 % by weight of the compound III from Example 1 275 0,75 % by weight of the compound VI from Example 2 272 Example 6:
Test for compatibility with sealant materials The test employed is the Volkswagen method VW-Seal test, P-VW 3334 at 150~C over a test period of 96 hours. The evaluated parameters are the change in the modulus 1/3 (at 1/3 elongation), the change in ultimate tensile strength and the change in elongation.

The test of a test material of the type FKM (fluorine rubber) in a motor oil containing either the compound of the formula III or a compound of the formula VI brings about no significant changes in the condition of the seals in respect of elongation and changes in tensile stress compared with the motor oil without the additives of the formulae III and VI.

Example 7:
Test of corrosion behaviour towards copper The Petter CEC L-02-A-78 test is used. The weight loss of copper bearings is determined after 36 hours, both in a phosphorus-free oil and in an oil containing phosphorus (P = 0.06 %) using a compound of the formula III
and a compound of the formula VI. The weight losses are less than 25 mg, thus complying with the requirements of the CCMC categories G 1, G 2 and G 3.

Claims

1. A compound of the formula in which R1 and R2 are identical or different and are tert-C4 to tert-C7alkyl or C5 or C6cycloalkyl, and Q is -S-, -S-S-, -S-CH2-S- or -S-CH2-CH2-S-.

2. A compound of the formula I according to claim 1, in which R1 and R2 are identical.

3. A compound of the formula I according to claim 1, in which R1 and R2 are tert-butyl or cyclohexyl.

4. A compound according to claim 1 selected of the groups of formulae , , , , , , , ,

5. A composition which comprises a) a functional fluid selected of the groups of lubricants, hydraulic fluids and metalworking fluids, and b) at least one compound of the formula I as defined in claim 1.

6. A composition according to claim 5 which comprises a) a lubricating oil selected of the groups of mineral oils, synthetic oils or mixtures thereof, and b) at least one compound of the formula I as defined in claim 5.

7. A composition according to claim 5 which comprises at least one compound of the formula I as defined in claim 5 in which R1 and R2 are identical.

8. A composition according to claim 7 which comprises at least one compound of the formula I as defined in claim 7 in which R1 and R2 are tert-butyl or cyclohexyl.

9. A composition according to claim 8 which comprises at least one compound selected of the groups of formulae , , , , , , , .

10. A composition according to claim 6, in which the lubricating oil is an oil for diesel or spark-ignition engines.

11. A composition according to claim 6 which conforms to API classification SF, SG, CD and/or CE or to CCMC categories G 1, G 2, G 3, D 1, D 2, D 3 and/or PD 1.

12. A process for reducing wear in diesel and spark-ignition engines, in which the lubrication system of the internal combustion engine is run on a lubricating oil having a composition according to claim 7.

13. A process for reducing wear on the cams of the camshafts and on the tappets of the valve train, in which the lubrication system of the internal combustion engine is run on a lubricating oil having a composition which comprises a compound of the formula (I) as defined in claim 1, in which R1 and R2 are identical and are tert-C4- to tert-C7alkyl or C5- or C6cycloalkyl, and Q is -S-, -S-S-, -S-CH2-S- or -S-CH2-CH2-S-.

14. A process for preventing the deactivation of the catalyst attached to the exhaust of a gasoline engine, in which the lubrication system of the internal combustion engine is run on a lubricating oil having a composition according to claim 7.

15. A process of making lubricants having improved multipurpose properties, comprising the step of adding to said lubricant an effective amount of a compound of the formula I
according to claim 1.

16. A process of making lubricants, hydraulic fluids or metalworking fluids having improved extreme-pressure and antiwear properties, comprising the step of adding to said lubricant an effective amount of a compound of the formula I
according to claim 1.