CA2002252C

CA2002252C - Lubricant compositions

Info

Publication number: CA2002252C
Application number: CA002002252A
Authority: CA
Inventors: Horst Zinke
Original assignee: Ciba Spezialitaetenchemie Holding AG
Current assignee: BASF Schweiz AG
Priority date: 1988-11-08
Filing date: 1989-11-06
Publication date: 1999-12-21
Anticipated expiration: 2009-11-06
Also published as: ES2055156T3; BR8905729A; EP0368803B1; KR0133932B1; EP0368803A1; HK127195A; MX172574B; JPH02182786A; CA2002252A1; KR900008016A; DE58904011D1; JP2855347B2

Abstract

Compositions containing a) a lubricant or a hydraulic fluid and b) an effective amount of a triaryl thionophosphate mixture of the formula I
in which x is 0 to 2.7, m is 3-(x+n) and n is 0 to 3-(x+m) and x+m+n is 3, R1, R2, R3, R4, R5, R6, R8 and R9, independently of one another, being, for example, H, alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, phenyl or phenyl-C1-C3alkyl and R4 and R7, independently of one another, being alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, phenyl or phenyl-C1-C3alkyl, subject to the proviso that x and n are nat 0 at the same time, that at least two of the radicals Ar1, Ar2 and Ar3 are different from one another and that dixylenyl paracresyl thionophosphate is excluded.
The triaryl thionophosphate mixtures are anti-wear additives and the compositions are particularly suitable, for example, for use in internal combustion machines.

Description

A-17292/=/CGM 338 Lubricant compositions The invention relates to novel lubricant and hydraulic fluid compositions containing triaryl thionophosphates and to the use of the triaryl thionophosphates in lubricants and hydraulic fluids as anti-wear additives.
A large number of triesters of thiophosphoric acid are known from French Patent 1,137,298 as antioxidants, anti-corrosion compositions and anti-wear and extreme pressure additives, for example in lubricants and other organic products. Other compositions containing aryl thionophosphates are also known, for example from German Auslegeschrift 1,288,224, which describes the diaryl alkyl or diaryl benzyl thionophosphates as high-pressure additives in lubricating oils, or from German Offenlegungsschri.ft 2,357,199, which mentions the anti-wear and high-pressure additives for lubricating oils. The latter additives are a mixture of the triesters of phosphonothionic acid, the esters of orthophosphoric acid and monoesters and diesters of phosphoric acid together with nitrogen-containing organic bases. Mixed triaryl thiophosphates which carry various aryl radicals and have at least one aryl radical of at least 9 C atoms are known from US Patent 2,250,049. This specific group of triaryl thiophosphates is suitable for use as a plasticizing agent and modifying agent for the preparation of various plastics.
Japanese Preliminary Published Application 61/26,696 describes an oil for metal machining containing triesters of thiophosphoric acid in order to reduce oxidation.
European Patent Application 0,245,852 describes a process for the preparation of liquid triaryl thiophosphate mixtures which are used in synthetic polymers as a fire-retarding composition.
Specific triaryl thionophosphate mixtures have now been found which display quite outstanding properties in compositions containing lubricants and hydraulic fluids and which stand out markedly in effectiveness compared with previously described compositions, for example in lubricating oils.

~r,~~~2~~

The present invention relates to compositions containing a) a lubricant or a hydraulic fluid and b) an effective amount of a triaryl thionophosphate mixture of the formula I
IArlO
?,rz Ol ~P = S (I) IAr30 L n in which x is 0 to 2.7, m is 3-(x+n) and n is 0 to 3-(x+m) and x + m + n is 3, ._,'/Ri Art is 3 Rz _ R°
/.
Ar2 is -o~ ,~ and R' Ar3 is _ i°~.~
y Re R1, R2, R3, RS, R6, Rg and R9 independently of one another being H, alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 Ct-C~alkyl groups, phenyl or phenyl-Ct-C3alkyl and R~ and R~, independently of one another, being alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 Ct-C4alkyl groups, phenyl or phenyl-Cl-C3alkyl, subject to the proviso that x and n are not 0 at the same time, that at least two of the radicals Art, Arz and Ar3 are different from one another and that dixylenyl paracresyl thionophosphate is excluded.
In the triaryl thionophosphate mixture of the abovementioned formula I it is advantageous forxtobe0to2.6,mtobe0.02to2.98andntobe0to2.98.

;~~,~~~~5~

A triaryl thianophosphate mixture of the abovementioned formula I in which x is 0.1 to 2.6, m is 0.1 to 2.9 and n is 0 to 2.8 is preferred.
In compounds of the formula I Art is preferably phenyl.
A triaryl thionophosphate mixture of the formula I in which Art is phenyl and x is 0.001 to 2.6 is advantageous.
In the triaryl thionophosphate mixture of the formula I Art is preferably phenyl and x is O.Olto2.6,mis0.02to2.99andnisOto2.97.
If the radicals Rl, R2, R3, R4, RS, R6, R~, Rg or R9 are alkyl having 1 to 18 C atoms, examples of these which should be mentioned are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, 1-methylpentyl, 1,3-dimethylbutyl, 2-ethylbutyl, heptyl, 3-heptyl, 1-methylhexyl, isoheptyl, octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 1-rnethylheptyl, nonyl, 1,1,3-trimethylhexyl, 3,5,5-trimethylhexyl, decyl, undecyl, dodecyl, 1-methylundecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. The radicals having 3 to 18 C
atoms can be present as straight-chain or branched-chain radicals or as mixtures of straight-chain and branched-chain radicals. Branched-chain radicals having 4 to 18 C atoms can, in addition, be mixtures of various isomeric structures. Examples of the alkyl radicals which are advantageous and preferred can be deduced analogously from the above list.
The radicals Rt to R9 are also cycloalkyl having 5 to 12 C atoms. The following should be mentioned as examples: cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.
The cycloalkyl groups having 5 to 12 ring C atoms can be substituted by 1 to 3 Ct-C4alkyl groups. Examples of these are 2-methylcyclohexyl, 4-methylcyclohexyl, dimethylcyclohexyl, trirnethylcyclohexyl or t-butylcyclohexyl. Cyclohexyl is preferred.
If the radicals Rt to R9 are phenyl-Ct-C3alkyl, examples which can be mentioned are benzyl, a-methylbenzyl or «,«-dimethylbenzyl.
If Rt, Rz, R3, R't, R5, R6, R~, Rg or R9 are a single substituent having one of the abovementioned meanings, except fox H, a 2-, 3-, 4-, 5- or 6-position on the corresponding ring Art, Arz or Are is possible, the 2-, 3- or 4-position is advantageous and the 2-position ~~~~a~~~

or 4-position is preferred, and, if two substituents are present on a particular ring, it is advantageous for the substituents to be arranged in the 2,4-position, while if three substituents are present in a particular ring, it is advantageous for them to be arranged in the 2,4,6-position.
In mixtures of the formula I it is advantageous for R4 to be Cl-Ctsalkyl, cyclohexyl, phenyl or phenyl-Ct-C3alkyl, for RS to be I-I or Ct-Cl2alkyl and for R6 to be H or Cl-Csalkyl.
In a particularly advantageous embodiment R4 is Cl-Cl2alkyl, cyclohexyl or phenyl-Cl-C3alkyl and RS and R6, independently of one another, are H or Ct-C4alkyl.
Preferably, R4 is C3-Cl2alkyl or ~yclohexyl and R$ and R6, independently of one another, are H or Cl-Cqalkyl.
It is particularly preferable for RS and R6, independently of one another, to be H or CI-I3.
It is very particularly preferable fox Ra to be C3-C9alkyl and for RS and R6 to be H.
The radical R4 is preferably in the ortho-position or para-position in the substituent Ar2.
RS and R6 are preferably H.
In mixtures of the formula I it is advantageous for R~ to be Cl-Ctsalkyl or cyclohexyl and for R$ and R9, independently of one another, to be H or Cl-Ci2alkyl.
It is particularly advantageous for R~ to be Cl-Cl2alkyl or cyclohexyl, for R8 to be I-I or Ci-Csalkyl and for R9 to be H or Cl-Cl2alkyl.
Preferably, R8 is H or Cl-CQalkyl and R9 is H or C1-Cloalkyl.
It is particularly preferable for R~ to be C3-Cloalkyl or cyclohexyl and for R8 and R9, independently of one another, to be H or Cl-C4alkyl.

The following are examples of triaryl thionophosphate mixtures of the formula I:
_. ._. ._. 0 p = S;
.\ /.__p_ \ / \
._. 0.01 ~~oH~9 ~~87 ~~loH2i 0.12 ~\._,/._p_ C~ ~/,_,%._p_ p = S;
0,60 \C~- 240 ._ . ~._~ ~._ ._p_ ~._p_p \ _0_ / _ ./ =
/ ~.=. ~ S

._ . 2,34C9Hi9 O~50 C 0.16 C'3/CHs %
\

j._p_ _ p ~ H S
C

\ /._0_ -. CH3_ /
~ ~\
\

. _, 1,74C 1,16 . _ 0,10 ~3\CH H' ~

~

,_ . _.\ ._0_ H3 ~._.\ p =
/ S;

\ 0 ~.=. CH3- _0_ / \
/

. _. CsHl9 H3 ._ '.~0 0.40 CH3 0,40 ~\
/

C
\CH
C~

C~I

/C\

._ . .-0- j._p_ CH3_ _.~~ p C ~~ H3\. aHs =
S;

._ . -, H3 _.
C .

2,25 ~ 0,7 0,05 \

C

._. ._. ._, p ~\ /~-0- \ / \ /
._. x~60 '~9H19 0,38 ioH2i 0,02 .tHl _ _ /~ ~\ _0-_ ~ ~\ 0 P = S;
-0- \ / \
~~H ~ 0,50 H3C-~-CHa 1,20 HZ 1,30 3 H3C_ _CH3 ._~ .-0_ ~ \ O CH3 H1 /._.\ _0_ p = S;
\ / H3 \._ / CH3 ~eHl~ p~15 _ ~~H1 2.70 \C/ 0,15 C~3\CHa ~_~ 0 ~~9H19 2.,8$ ~~1OH21 0,12 /~- \ ._. 0 ~.-~\ o p S
.\ / _0_ .\ /. .\ /.
._. ~~30 ~~9H19 0,67 ~~1oH21 0,03 _.\ - H3 \ /._0_ /. .\ ._.\ .\. 'j._p_ p = S.
'/ \ _ ~.- -.
.~lsHj1 1,00 ' ' H3 ._. 0,05 ~~BH1~ 1,95 Examples which should be mentioned particularly are compositions containing at least one triaryl thionophosphate mixture from the series having the formulae .; j._0_ p . -S;

\ , .

2,00 ~9H19 0,96 ~1oH21 0,04 C; p S.
r:_:;._0_ ~
;

_ ~

0., /C ~, H
\

_ C
\

._ . C OH3 P S
\ 0 , CH3-/ ._0_ H3 ~._.\
.
~

._ . 1,74 C 1,16 \_,/ 0,10 C~ H
\ ' CF\I CH

CH C~I

C

\

._ .\ ._. /._.\ CH1 \ / \ / 0 \ / ~ p . ~ S, .

_ 2,00 ._. 0~5 ._. 0.5 _7_ or j t13 ~._~~._p_ CHl H3 /._.\ - P -'\ /' ._. C H19 .. H3 \.-./~ CH;
2,20 0,40 \C/ 0,40 CH3\CH~
._. ~'_~~ _ _ C ~' ' ._ _ p -_p_ /. /
\._./~ 234 C9Hi9~.-. p'Sp ~C~ ._. p~16 and /._~~._p_ ~~_~ p P = S.
\ /
._. 200 ~~sHi3 1.00 The triaryl thionophosphate mixtures can be prepared by methods known per se.
Reference is made, for example, to Houben-Weyl "Methoden der Organischen Chemie"
["Methods of Organic Chemistry"], volume 12, part 2, pages 623-652 (G. Thieme Verlag, Stuttgart, 1960 or to G.M. Kosolapoff and L. Maier, "Organic Phosphorus Compounds", volume 7, pages 482-871 and particularly pages 717-722 (John Wiley & Sons, New York, 1976).
As a rule the reaction is earned out by using the alkylphenol or phenol/alkylphenol mixture as starting material and first synthesizing the corresponding triaryl phosphite mixture by means of phosphorus trichloride and then in turn reacting this mixture with sulfur to give the triaryl thionophosphate mixture.
This reaction follows the general equation:

~ . .~e .
~ R ~ . R
x . / \ -OH + m / \ -OH + n / \ -OH
3 6 ~9 -8- ' -o RZ,C.y /
:C
1. PC1~/-3 HC1 -0 P = S
2. S R ,(, /
. .
X .-p Re~~~9 n in which Rt, R2, R3, R4, R5, R6, R~, R8 and R9 and also x, m and n are as defined above.
The resulting triaryl thionophosphate mixtures can be purified by washing with alkali and, as a rule, are clear, in some cases coloured, liquids of an oily consistency which can, for example, be incorporated readily into various oil formulations.
Since the triaryl thionophosphate mixtures are, in practice, technical products, they can be accompanied by traces of triaryl thionophosphates which are not expressly mentioned. For example, in compounds of the formula I in which x is 0, traces of a triaryl thionophosphate mixture containing an unsubstituted phenyl radical can, nevertheless, be present.
The compositions according to the present invention can contain one or more of the triaryl thionophosphate mixtures of the formula I.
In compositions according to the present invention the triaryl thionophosphate mixture can be used in proportions of 0.01 to 10, advantageously 0.05 to 5, preferably 0.05 to 3 and particularly 0:1 to 2, % by weight, relative to the lubricant or the hydraulic fluid.
As mentioned initially, the compositions according to the invention contain a lubricant or a hydraulic fluid and the triaryl thionophosphate mixture.
The products known per se are used as lubricants or hydraulic fluids.
The lubricants and hydraulic fluids which are suitable are well known to those skilled in the art and are described, for example, in Dieter Klamann "Schmierstoffe and verwandte Produkte" ["Lubricants and related products"), Verlag Chemie, Weinheim, 1952, in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" ["The lubricant handbook"~, Dr.

Alfred Hiithig-Verlag, Heidelberg, 1974, or in "Ullmanns Encyclopadie der technischen Chemie" ["Ullmann's encyclopaedia of industrial chemistry"], volume 13, pages (Verlag Chemie, Weinheim, 1977).
Examples of these are lubricants and hydraulic fluids based on mineral oils or synthetic lubricants or hydraulic fluids, particularly those which are carboxylic acid ester derivatives and are used at temperatures of 200°C and above. Other hydraulic fluids are oil-in-water or water-in-oil systems, and also aqueous systems.
Examples of synthetic lubricants embrace lubricants based on a diester of a dibasic acid with a monohydric alcohol, for example dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monobasic acid or with a mixture of such acids, for example trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monobasic acid or with a mixture of such acids, for example pentaerythritol tetracaprylate or a complex ester of monobasic and dibasic acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic acid and sebacic acid ox of a mixture thereof.
Besides mineral oils, examples of particularly suitable lubricants are poly-a-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, and also mixtures thereof with water.
Compared with known products, such as zinc dithiophosphate, O,O-dialkyl S-alkyl dithiophosphates, tricresyl phosphate and the like, the compositions according to the invention exhibit good anti-wear properties in the whole temperature range in which they are used, at a reduced content of phosphorus and sulfur. Tn particular above a temperature range of 150°C, the present compositions are superior to conventional products. This is of great significance, since in internal combustion engine technology for example, the lubricants too are subject to increased demands as development progresses, and are subject to relatively high temperatures for relatively, long periods. At a relatively high temperature, the known additives are not capable of developing any anti-wear effect, or only an insufficient effect.
The present invention also relates to the use of the abovementioned copposition as an anti-wear additive in lubricants and hydraulic fluids. For the purposes of use, the composition is advantageously used at temperatures from 60 to 200°C, and preferably for ~'~~~~e~re~'.~~

temperatures from 100 to 180°C. The compositions are very particularly preferably used for application puzposes at temperatures from 150 to 180°C.
The compositions according to the invention are advantageously suitable for use as lubricating oil compositions for internal combustion machines in general, i.e.
for engines working on the diesel principle and for engines working on the Otto principle.
The term Otto principle is to be understood as meaning internal combustion machines with spark ignition working on the piston principle. The internal combustion machines can serve the known purposes, that is to say, for example, for use as stationary engines or as propulsion in means of transport, such as ships, aeroplanes and especially motor vehicles.
The invention can thus also relate to compositions in which the lubricating oil is an oil for internal combustion machines operating on the diesel or Otto principle.
The invention relates especially to lubricating oil compositions of the type mentioned containing a triaryl thionophosphate mixture of the foranula I, as previously described, of API classification SF, SG, CD and/or CE or of CCMC classes G 1, G 2, G 3, D 1, D 2, D 3 andJor PD 1.
Accordingly, the compositions are advantageously engine oils for motor vehicles, and in this regard essentially for passenger car engines and commercial vehicle engines, which correspond in the API classification (American Petroleum Institute) to at least one of the categories having the characteristic letters SF, SG, CD or CE and in the CCMC
classification (Committee of Common Market Automobile Constructors) to at least one of theclassesG 1,G2,G3,D 1,D2,D3orPD 1.
The lubricants and hydraulic fluids can contain, in addition, other additives which are added in order to improve the fundamental properties of lubricants. These include:
antioxidants, metal deactivators, rust inhibitors, viscosity index improvers, pour-point depressors, dispersing agents, detergents, high-pressure additives and other anti-wear additives.
The following are examples of these:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tart-butylphenol, 2,6-di-tart-butyl-4-dimethylphenol, 2-tart-butyl-4,6-dimethylphenol, 2,6-di-tart-butyl-4-ethylphenol, 2,6-di-tart-butyl-4-n-butylphenol, 2,6-di-tart-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tart-butyl-4-methoxymethylphenol or 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones, for example 2,6-di-tart-butyl-4-methoxyphenol, 2,5-di-tart-butylhydroquinone, 2,5-di-tart-amylhydroquinone or 2,6-diphenyl-4-octadecyloxyphenol.
1.3. H~droxylated thiodiphenyl ethers, for example 2,2'-thio-bis-(6-tart-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tent-butyl-3-methylphenol) or 4,4'-thio-bis-(6-tart-butyl-2-methylphenol).
1.4. Alkylidene bisphenols, for example 2,2'-methylene-bis-(6-tart-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tart-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(a-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-tart-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tart-butylphenol), 2,2'-ethylidene-bis-(6-tent-butyl-4-isobutylphenol), 2,2'-methylene-bis-[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(«,«-dimethylbenzyl)-4-nonylphenol, 4,4'-methylene-bis-(2,6-di-tart-butylphenol), 4,4'-methylene-bis-(6-tart-butyl-2-methylphenol), 1,1-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-bis-(3-tart-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris-(5-tart-butyl-4-hydroxy-2-rnethylphenyl)-butane, 1,1-bis-(5-tent-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3'-tart-butyl-4'-hydroxyphenyl)-butyrate], bis-(3-tent-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene or bis-[2-(3'-tent-butyl-2'-hydroxy-5'-methylbenzyl)-6-tent-butyl-4-methylphenyl]
terephthalate.

1.5. Benzyl compounds, fox example 1,3,5-tris-(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-tort-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the Ca salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ar 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bis-(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine or octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
1.7. Esters of ~-(3,5-di-tert-but ~Ll-4-h d~yphenyl)-propionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)-isocyanurate or N,N'-bis-(hydroxyethyl)-oxamide.
1.8. Esters of R-(5-tert-butyl-4-hydroxy-3-methylphen~pro~ionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate or N,N'-bis-(hydroxyethyl)-oxamide.
1.9. Esters of a-(3,5-dicyclohexyl-4-hydroxyphenyl)-propianic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanedial, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate or N,N'-bis-(hydroxyethyl)-oxamide.
1.10. Amides of p-(3,S-di-tert-bull-4-hydroxyphen~propionic acid, for example N,N'-bis-(3,5-di-tert-butyl-4-hydraxyphenylpropionyl)-hexamethylenediamine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine or N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

2. Examples of amine antioxidants: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis-(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis-(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-(naphth-2-yl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-phenylenediamine, 4-(p-toluenesulfonamido)-diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylarninophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di-(4-methoxyphenyl)-amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetrarnethyl-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-1-naphthylamine, mixture of monoalkylated and dialkylated tert-butyldiphenylamines/tert-octyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine or N-allylphenothiazine.
3. Examples of other antioxidants: Aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbamic or dithiophosphoric acid.
4. Examples of metal deactivators, for example for copper, are as follows:
triazoles, benzotriazoles and derivatives thereof, tolutriazoles and derivatives thereof, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidenepropylenediamine or salicylaminoguanidine and salts thereof.

n~i2~~~

5. Examples of mst inhibitors are as follows:
a) Organic acids and their esters, metal salts and anhydrides, for example N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, an alkenylsuccinic anhydride, for example dodecenylsuccinic anhydride; alkenylsuccinic acid partial esters and partial amides or 4-nonylphenoxyacetic acid.
b) Nitrogen-containing compounds, for example:
I. Primazy, 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) Phosphorus-containing compounds, for example: amine salts of phosphoric acid partial esters or phosphonic acid partial esters or zinc dialkyl dithiophosphates.
d) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates or calcium petroleumsulfonates.
6. Examples of viscosity index improvers are as follows: polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers or polyethers.

7. Examples of pour-Qoint depressors are as follows: polymethacrylate or alkylated naphthalene derivatives.

8. Examples of dispersing_agents/surfactants are as follows:
polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives or basic magnesium, calcium and barium sulfonates and phenates.

9. Examples of other anti-wear additives are as follows: compounds containing sulfur and/or phosphorus and/or halogen, such as sulfurized vegetable oils, zinc dialkyl dithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides and trisulfides, other triphenyl phosphorothionates, diethanolaminomethyltolyltriazole or di-(2-ethylhexyl)-aminomethyltolytriazole.
The following examples illustrate the invention in greater detail, without limiting it. Parts and percentages are by weight, unless stated otherwise.
Example 1: Phenyl non~phenyl decylphenyl thionophosphate mixture.
1 mol of phosphorus trichloride is added dropwise in the course of 2-3 hours, with stirring and at room temperature, to a mixture of 2 mol of phenol, 0.96 mol of nonylphenol, 0.04 mol of decylphenol and 0.03 mol of diethylamine (catalyst). After the evolution of hydrogen chloride has subsided, the reaction mixture is heated up slowly and is stirred for 8 hours at 140°C. Unreacted portions of phenol and residual hydrogen chloride are then removed by stirring for 2 hours at 140°C in vacuo.
1.03 mol of sulfur (sublimed) are added to the phosphite mixture thus obtained, and the mixture is heated up slowly with stirnng to 110-120°C and is stirred for 2 hours at this temperature and for 6 hours at 140-150°C.
After cooling, the mixture is diluted with toluene and the resulting phenyl nonylphenyl decylphenyl thionophosphate mixture of the formula ,._.~ ~0- ~ ,._., ~"~ .".
2,00 ~~~ 0,,96 ~~~ 0,04 eHl9 ioHzi is washed with sodium hydroxide/sodium sulfate solution (10 % + 10 %) and dried with anhyd-rows sodium sulfate, and the solvent is removed by vacuum distillation.
Yield: 417.5 g (89.1 % of theory) of a yellow liquid nD : 1.5582 % P 6.61 calculated 6.58 found Example 2: Phen,~ o-t-butylphen 1-y o-isopropylphenyl thionophosphate mixture.
A mixture of 2 mol of phenol, 0.5 mol of o-t-butylphenol and 0.5 mol of o-isopropylphenol is reacted, as described in Example l, with 1 mol of phosphorus trichloride and then with 0.95 mol of sulfur.
The resulting thionophosphate mixture of the formula c~,/cH3 CH3 C C~1 ._. /._. NCH; ~._.\ CH3 .\ /._0_ ,\ /._0_ \ / 0 P S
~ 2,00 ~ ~ 0,5 ~ ~ 0,5 is purified by washing with alkali and dried, and the solvent is distilled off.
Yield: 332.9 g (85 °lo of theory) of a pale yellow liquid nD : 1.5794 % P 7.91 calculated 8.00 found Example 3: Phenyl hexylphenyl thionophosphate mixture 1 mol of 1-hexene is added dropwise slowly at 90°C to a mixture of 3 mol of phenol and 0.072 mol of concentrated sulfuric acid, and the mixture is stirred fox 2 hours at 95-100°C.
The resulting reaction mixture of phenol and hexylphenol is then reacted, as described in Example 1, with 1 mol of phosphorus trichloride and 1 mol of sulfur.
As described, the thionophosphate mixture of the formula _p_ ~\._~~._0_ p ._. x,00 '~~ 1.00 is purified by washing with alkali and dried, and the solvent is distilled off.
Yield: 304.5 g (71 % of theory) of a pale brown liquid nD : 1.5635 % P 7.26 calculated 7.16 found The triaryl thionophosphate mixtures (Example 4-11) collated in Table 1 below are prepared by the process described in Example 1 or Example 3.

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Examples 12-15: Anti-wear and frictional behaviour of the triar~ thionovphos~te mixtures - Anti-wear/extreme pressure additives exhibit a characteristic behaviour under the application of friction, which is determined as a function of the temperature:
above a certain temperature at which the arrangement of protective reaction layers is no longer ensured, an abmpt change takes place in the so-called wear maximum. The wear maximum is characterized by the fact that substantially higher wear values appear and, in addition, very often worse coefficients of friction as well. On the basis of the present state of knowledge it is not possible to make precise statements concerning the conditions under which this abrupt change takes place.
- The AW/EP additives are characterized by means of the vibration-friction-wear instrument [SRV instrument German .Patent Specification 1,648,597, compare Lubrication Engineering, volume 39, No. 11 (Nov. 1982) Advertising Index, Cover 3], which is based on the following principle of measurement:
A steel ball on which a vertical force F~ acts describes an oscillating sliding motion on a steel cylinder. The horizontal and vertical forces are measured by means of a piezoelectric force transducer. A few drops of oil containing 2 % by weight of a compound to be examined are applied between the ball and the cylinder. The coefficient of fi-iction and the wear can be determined simultaneously by means of this test. The wear is characterized by taking a cross-section with a feeler-cutting instrument (Talysurf 10), and measuring the integrated surface of the cross-section as a measure of the wear. The values of wear quoted are therefore relative values of wear. The values are determined in em2 x 0.2 x 10-S. High values mean considerable wear.
The base oil used in each case is a mineral oil ISO VG 32.

- The anti-wear action of the triaryl thionophosphate mixtw..s according to the invention is shown in Table 2 below in comparison with unalloyed base oil. In each case 2 %
by weight of the particular compound to be tested are added to the above base oil before the test.
Table 2 SRV wear measurements Wear:cm2 x 0.2 x 10'5 Example Compound from Exam- SRV wear ple (2 % by weight relative to the base 100C 150C

oil 12 4 1.3 4.6 13 3 1.1 6.2 14 6 1.2 4.0 15 10 0.8 4.3 16 Base oil Comparison ISO VG 32 14.0 24.6

Claims

1. A composition containing a) a lubricant or a hydraulic fluid and b) an effective amount of a triaryl thionophosphate mixture of the formula I
in which x is 0 to 2.7, m is 3-(x+n) and n is 0 to 3-(x+m) and x+m+n is 3, Ar1 is Ar2 is Ar3 is R1, R2, R3, R5, R6, R8 and R9 independently of one another being H, alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 C1-C4alkyl groups, phenyl or phenyl-C1-C3alkyl and R4 and R7, independently of one another, being alkyl having 1 to 18 C atoms, cycloalkyl having 5 to 12 C atoms, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 C1-C4alkyl groups, phenyl or phenyl-C1-C3alkyl, subject to the proviso that x and n are not 0 at the same time, that at least two of the radicals Ar1, Ar2 and Ar3 are different from one another and that dixylenyl paracresyl thionophosphate is excluded.

2. A composition according to claim 1, wherein, in mixtures of the formula 1, x is 0 to 2.6, m is 0.02 to 2.98 and n is 0 to 2.98.

3. A composition according to claim 1, wherein, in mixtures of the formula 1, x is 0.1 to 2.6,m is 0.1 to 2.9 and n is 0 to 2.8.

4. A composition according to claim 1, wherein, in mixtures of the formula I, Ar1 is phenyl.

5. A composition according to claim 4, wherein, in mixtures of the formula I, x is 0.001 to 2.6.

6. A composition according to claim 5, wherein, in mixtures of the formula I, x is 0.01 to 2.6, m is 0.02 to 2.99 and n is 0 to 2.97.

7. A composition according to claim 1, wherein, in mixtures of the formula I, R4 is C1-C15alkyl, cyclohexyl, phenyl or phenyl-C1-C3alkyl, R5 is H or C1-C12alkyl and R6 is H
or C1-C5alkyl.

8. A composition according to claim 7, wherein R4 is C1-C12alkyl, cyclohexyl or phenyl-C1-C3alkyl and R5 and R6, independently of one another, are H or C1-C4alkyl.

9. A composition according to claim 8, wherein R4 is C3-C12alkyl or cyclohexyl and R5 and R6, independently of one another, are H or C1-C4alkyl.

10. A composition according to claim 9, wherein R5 and R6, independently of one another, are H or CH3.

11. A composition according to claim 9, wherein R4 is C3-C9alkyl and R5 and R6 are H.

12. A composition according to claim 1, wherein, in compounds of the formula I, the radical R4 is in the ortho-position or para-position in the substituent Ar2.

13. A composition according to claim 1, wherein, in compounds of the formula I, R7 is C1-C15alkyl or cyclohexyl and R8 and R9, independently of one another, are H
or Ct-C12alkyl.

14. A composition according to claim 13, wherein R7 is C1-C12alkyl or cyclohexyl, R8 is H or C1-C5alkyl and R9 is H or C1-C12alkyl.

15. A composition according to claim 14, wherein R8 is H or C1-C4alkyl and R9 is H or C1-C10alkyl.

16. A composition according to claim 14, wherein R7 is C3-C10alkyl or cyclohexyl and R8 and R9, independently of one another, are H or C1-C4alkyl.

17. A composition according to claim 1, containing at least one triaryl thionophosphate mixture from the series having the formulae

18. A composition according to claim 1 containing a) a lubricating oil from the series of mineral oils, synthetic oils or mixtures thereof, and b) at least one triaryl thionophosphate mixture of the formula I.

19. A composition according to claim 18, wherein the lubricating oil is an oil for internal combustion machines working on the diesel or Otto principle.

20. A composition according to claim 18 of the API classification SF, SG, CD
and/or CE
or of the CCMC classes G1, G2, G3, D1, D2, D3 and/or PD 1.

21. A composition according to claim 1 for applications at temperatures from 60 to 200°C.

22. A composition according to claim 1 fox applications at temperatures from to 180°C.

23. A process of making a lubricant or hydraulic fluid having improved anti-wear properties, comprising the step of adding to said lubricant or hydraulic fluid an effective amount of a triaryl thionophosphate mixture of the formula I according to claim 1.