Ciba-geigy Corporation

Ciba Specialty Chemicals Corporation

Rolf Schumacher

Horst Zinke

Samuel Evans

Paul Dubs

Hermann O Wirth

Hugo Camenzind

Klaus Muller

Arnold Grubenmann

Bisdithiophosphoric acid derivatives as lubricant additives

There are disclosed compounds of formula I ##STR1## R.sub.1 and R.sub.2 are each independently of the other C.sub.3 -C.sub.18 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.5 -C.sub.6 cycloalkylmethyl, C.sub.9 -C.sub.10 bicycloalkylmethyl, C.sub.9 -C.sub.10 tricycloalkylmethyl, phenyl, C.sub.7 -C.sub.6 alkylphenyl or, taken together, are ##STR2## R.sub.3 is hydrogen or methyl, A is ##STR3## R.sub.4 is hydrogen or C.sub.1 -C.sub.6 alkyl, and R.sub.5 is a 5- or 6-membered saturated heterocyclic ring, R.sub.6 is hydrogen or methyl, n is an integer from 1 to 11 and m is an integer from 0 to 4. These compounds are particularly suitable for use as additives for lubricant compositions, hydraulic fluids and machining fluids.

Dithiophosphoric acid derivatives as lubricant additives

There are disclosed compounds of formulae I and Ia ##STR1## wherein R.sub.1 and R.sub.2 are each independently of the other C.sub.1 -C.sub.13 alkyl which may be interrupted by oxygen, C.sub.5 -C.sub.6 cycloalkyl or, together with the linking N-atom, are a group of formula ##STR2## R is hydrogen or methyl, R.sub.3 is hydrogen or C.sub.1 -C.sub.13 alkyl, and

Trisamidodithionodiphospates

A lubricant based on a mineral or synthetic oil is stabilized against oxidative degradation by the addition of a mixture comprising at least one specified aromatic amine of the formula I or II ##STR1## and at least one sterically hindered amine. The lubricant may contain other antioxidants or other additives. It is preferably used as motor oil.

Lubricant composition

Lubricant compositions free of barium salt are described, which comprise A) a lubricant, B) at least one compound of the formula I ##STR1## in which R.sub.1 and R.sub.2, independently of one another are C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.18 alkenyl, phenyl, phenyl substituted by C.sub.1 -C.sub.20 alkyl, phenyl-C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.12 hydroxyalkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.5 -C.sub.12 cycloalkyl substituted by C.sub.1 -C.sub.4 alkyl, or naphthyl and Y represents O or S, and C) at least one compound of the formula II, III, or IV ##STR2## in which n is a number from 1 to 4, R.sub.3 is hydrogen, oxyl, hydroxyl, C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, phenyl-C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.8 cycloalkoxy, C.sub.7 -C.sub.9 phenylalkoxy, C.sub.2 -C.sub.8 alkanoyl, C.sub.3 -C.sub.5 alkenoyl, C.sub.2 -C.sub.18 alkanoyloxy, benzyloxy, glycidyl or a group --CH.sub.2 CH(OH)--Z in which Z is hydrogen, methyl or phenyl, and, if n is 1 R.sub.4 is hydrogen, C.sub.1 -C.sub.18 alkyl or C.sub.2 -C.sub.18 alkyl which is interrupted by one or more oxygen atoms, C.sub.3 -C.sub.8 alkenyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic or cycloaliphatic, araliphatic or aromatic carboxyylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, if n is 2 R.sub.4 is C.sub.1 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or a phosphorus-containing acid or a divalent silyl radical, if n is 3 R.sub.4 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, if n is 4, R.sub.4 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid, and R.sub.8 is C.sub.1 -C.sub.18 alkyl or a polyisobutylene radical, and R.sub.9 is C.sub.1 -C.sub.8 alkyl. The compositions serve to improve the use properties of the corresponding lubricant and have in particular good resistance to oxidation at high temperatures.

Lubricant compositions

Formulation containing A) a lubricant and a mixture of B) for example, at least one of the compounds O,O-bis-2-ethylhexylsodium dithiophosphate, O,O-bis-2-ethylhexylsodium thionophosphate, O,O-bis-2-methylpropylsodium dithiophosphate, O,O-bis-nonylphenylsodium dithiophosphate or S-[O,O-bis-2-ethylhexylthiophosphoryl]-potassium thioglycolate, C) at least one compound from the series of the aromatic amines, for example the diphenylamines or phenothiazines, and D) at least one compound from the series of the cyclic sterically hindered amines, the acyclic sterically hindered amines and the phenols of the formula ##STR1## wherein R.sup.4, R.sup.5 and A are, for example, alkyl radicals. Such lubricant formulations have a high degree of stability towards oxidative degradation.

Lubricant formulations

Phosphite-free lubricating oil composition which comprises a) a mineral oil or a synthetic oil or a mixture thereof, and b) a mixture containing at least one aromatic amine of the formula (I), ##STR1## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.3 ' are as defined in claim 1, and at least one phenol of the formula ##STR2## in which R.sup.4, R.sup.5 and A are as defined in claim 1, and the compounds are present in the mixture in a ratio of 2 to 6 parts by weight of the aromatic amine(s) of the formula I to 1 part by weight of the phenol(s) of the formula II. The lubricating oil compositions are highly resistant to ageing and are effective in preventing black sludge formation.

Lubricating oil composition

A lubricant based on a mineral or synthetic oil is stabilized against oxidative degradation by the addition of a mixture comprising at least one specified aromatic amine of the formula I ##STR1## and at least one sterically hindered amine. The lubricant may contain other antioxidants or other additives. It is preferably used as motor oil.

High-temperature lubricants

Compounds of formula I ##STR1## wherein R and R.sup.1 are identical or different and are a radical of the formula ##STR2## where R.sup.2, R.sup.3 and R.sup.4 are each independently C.sub.1 -C.sub.18 alkyl and together contain not more than 22 carbon atoms, and R.sup.3 and R.sup.4 are also hydrogen, or wherein R and R.sup.1 are C.sub.5 -C.sub.6 cycloalkyl, unsubstituted or C.sub.1 -C.sub.4 alkyl-substituted phenyl, or naphthyl, C.sub.7 -C.sub.14 aralyl, furfuryl or thienyl, and wherein Y is --S--, --O--, --NH--, --N(C.sub.1 -C.sub.12 alkyl)--, --CH.sub.2 --, --CH(C.sub.1 -C.sub.12 alkyl)-- or --C(C.sub.1 -C.sub.12 alkyl).sub.2 -- and X.sup..sym. is 1 equivalent of a metallic cation selected from the group consisting of Li.sup..sym., Na.sup..sym., K.sup..sym., Mg.sup.2.sym., Ca.sup.2.sym., Ba.sup.2.sym., Zn.sup.2.sym., Mn.sup.2.sym., Ni.sup.2.sym., Fe.sup.3.sym., Fe.sup.2.sym., Co.sup.2.sym., Cu.sup.2.sym., Al.sup.3.sym., Cr.sup.3.sym., VO.sup. 3.sym., ZrO.sup.2.sym., MoO.sub.2.sup.2.sym. and TiO.sup.2.sym., are suitable as additives for lubricants and hydraulic oils and bring about an improvement in the extreme-pressure properties and in the anti-wear properties.

Boric acid complexes

Lubricant compositions containing (a) a mineral and/or synthetic base oil and (b) at least one compound of the formula I ##STR1## wherein a is 0 or 1, b is 1 to 6, R is H or alkoxycarbonyl, R.sup.1 and R.sup.2 are independently alkyl, cycloalkyl, aryl, aralkyl or are together substituted alkylene and X is hydroxyl, alkoxy, aryloxy, amino, substituted amino or the residue of a polyol, are described.

The load-carrying capacity of liquid lubricants having a kinematic viscosity of 2 to 1500 mm.sup.2 /s at 40.degree. C. can be substantially improved by the addition of oil-insoluble, dispersible aromatic compounds which are chlorine-substituted in the nucleus. The compounds, which consist of 1 to 4 completely unsaturated or partially saturated aromatic moieties which may contain hetero-atoms and are linked to one another through a simple direct bond, a double bond or through --O--, --S--, --N(R)--, --N.dbd., alkylene, --NHCO--, --N.dbd.CH--, --N.dbd.N--, --N.dbd.NCH(COCH.sub.3)CONH, --CH.dbd.N--N.dbd.CH-- or .dbd.N--(Y)--N.dbd., contain from 2 to 24 aromatic chlorine atoms. The combination of the additives of the invention with conventional antiwear additives has been found to be particularly advantageous.

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Marly, Switzerland

Rolf Schumacher