This invention relates to a lubricant composition containing a combination of additives providing antiwear properties, and to the antiwear additive combination contained therein.

It is well-known to include an antiwear additive in lubricating oils such as engine oils. Wear results mainly from the rubbing together of two metal surfaces, i.e. in boundary lubrication regimes, such as is found in valve trains in internal combustion engines. It is believed that the antiwear additive acts to provide a protective film over the metal surfaces. One well-known class of antiwear additives is the metal alkylphosphate, especially zinc dialkyldithiophosphate ("ZDDP"). Generally ZDDP is employed at treat levels of 1 to 2 wt.% based on the total weight of the lubricant, which gives a phosphorus level in the lubricant typically in the range of from 0.05 to 0.15 wt.%, and a zinc level of from 0.1 to 0.2 wt.

In recent years there has been increasing concern that lubricant ash levels, such as that produced by the zinc in ZDDP, contribute to particulate emissions from internal combustion engines. There is also concern that the phosphorus from the lubricant tends to poison catalysts used in catalytic converters, thereby preventing them from functioning to full effect. However, any reduction in ZDDP treat levels has the disadvantage that it will reduce the antiwear properties of the lubricant.

There is therefore a need for an effective antiwear additive with reduced zinc and phosphorus levels.

We have found that a phosphorus-free organo-molybdenum compound and an ashless sulphur-containing organo-phosphorus compound act together synergistically to provide improved antiwear performance when used in a lubricant composition. By using this combination of compounds it becomes possible to achieve the same or better performance than that achieved with ZDDP, with significantly lower levels of phosphorus.

Sulphur-containing organic phosphorus compounds are known to be used as "extreme pressure compounds" in heavy duty applications such as greases for constant velocity joints. It is also known to use sulphur-containing organic compounds of heavy metals such as molybdenum, tungsten and lead in such applications. Thus GB-A-2255346 describes an additive for grease used in constant velocity joints comprising in combination molybdenum sulphide dialkyldithiocarbamate, zinc dithiophosphate, a sulphur-phosphorus series extreme pressure

US-A-4648985 describes a lead-free extreme pressure additive, generally for lubricants based on asphalt, utilising an organic phosphate in combination with copper or molybdenum compounds selected from carboxylate, phosphate, thiophosphate and thiocarbamate, optionally with a metal-free thiocarbamate or in combination with a metal thiocarbamate (numerous metals being described). The preferred metals are copper and zinc.

Organic phosphorus compounds are also used as ashless dispersants. Thus EP-A-

0516461 describes a dispersant additive for lubricating oils showing improved compatibility with elastomeric seal material which comprises in combination a metal dihydrocarbyl dithiocarbamate or dithiocarbamate and a phosphorylated ashless dispersant. Various metal compounds are described including molybdenum dithiophosphate.

EP-A-0316610 describes a multipurpose antiwear, antiseizure and corrosion inhibiting additive for lubricating oils utilising a combination of an organo-phosphorus compound selected from various phosphines and phosphites and an organo-molybdenum compound selected from oxysulphide alkylphosphorodithioates and oxysulphide alkyl dithiocarbamates.

GB-A- 1373588 describes an antiwear, antioxidant additive combination comprising a metal dialkyldithiocarbamate and/or a metal alkyl, aryl or aralkyl dithiophosphate and a metal- free phosphorus compound selected from sulphurised sperm oil esterified with dithiophosphate, sulphurised terpene esterified with dithiophosphate, sulphurised and phosphated sperm oil and phosphorus polysulphide. Many metals are mentioned including molybdenum, zinc and lead.

In one aspect the present invention provides a lubricant composition comprising a base oil of viscosity from 3 to 26 cSt (mra^/s) at 100°C and an antiwear additive combination comprising (a) an oil soluble or oil dispersible phosphorus-free organo-molybdenum compound and (b) an ashless sulphur-containing organo-phosphorus compound.

Furthermore, we have found surprisingly that compounds (a), (b) when used in combination with reduced levels of a selected zinc thiophosphate, act synergisticaUy to provide better wear protection than that achieved using a comparable amount (i.e. an amount providing a similar total level of phosphorus) of the zinc thiophosphate alone.

Accordingly in a preferred lubricant composition the combination includes, in addition to (a) and (b), a zinc thiophosphate compound (c) selected from one or more of zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc alkylaryldithiophosphate and zinc arylalkyldithiophosphate.

This provides the advantage that the organo-molybdenum compound can replace some

of the zinc thiophosphate compound used in lubricant compositions with the effect that the phosphorus level in the lubricant is reduced without substantially reducing, indeed increasing the antiwear performance of the lubricant.

The organo-molybdenum compound may comprise a molybdenum carbamate, preferably a dicarbamate and more preferably a dithiocarbamate (MoDTC) the organo group(s) of which may be substituted with a hydrocarbyl groups and or one or more hetero atoms, with the proviso that the organo group selected results in an organo-molybdenum compound that is oil-soluble or oil-dispersible, preferably oil-soluble.

However it is known that MoDTC decomposes when heated in use to decomposition products which include free amine and carbon disulphide. Both such products are aggressive towards copper which is present in the engine bearings. Wear in bearings is particularly objectionable since repair involves complete dismantling of the engine. Carbon disulphide tends to boil off fairly rapidly and does not constitute a special problem. However even small amounts of free amine can cause damage.

We have found that the synergisms described above extend not only to carbamates of molybdenum but also to molybdenum compounds which are nitrogen free and which therefore do not decompose to free amine. A preferred organo-molybdenum compound is also free from sulphur.

Accordingly in a preferred combination of (a) and (b) together optionally with (c) the organo-molybdenum compound is nitrogen-free. It is preferably selected from a carboxylate and a xanthate or mixtures thereof the organo group(s) of which may be substituted with a hydrocarbyl group, again with the proviso that the organo group selected results in an organo- molybdenum compound that is oil-soluble or oil-dispersible, preferably oil-soluble.

The preferred organo-molybdenum compound comprises a carboxylate. Not only do such compounds contain no nitrogen or phosphorus but they are relatively cheap and contain a higher proportion of molybdenum than the more complex compounds. As will be described in more detail, it is believed that the effective additive content is governed by the metal content. Thus only about one third of the amount e.g. of molybdenum 2-ethyl hexanoate need be used by comparison with molybdenum dithiocarbamate.

In another aspect the present invention provides an antiwear agent comprising a combination of (a) an organo-molybdenum compound as above described, (b) an ashless organo- phosphorus compound as above described and, optionally, (c) a zinc thiophosphate as above

described.

In a further aspect the present invention provides the use in a lubricant composition of the combination of (a) an organo-molybdenum compound as above described, (b) an ashless organo-phosphorus compound as above described and, optionally, (c) a zinc thiophosphate as above described, as an antiwear agent.

In a yet further aspect the invention provides an additive concentrate comprising in combination: (a) an organo-molybdenum compound as above described, (b) an ashless organo- phosphorus compound as above described, optionally (c) a zinc thiophosphate as above described and a carrier fluid.

Where the organo group is a carbamate, the organo-molybdenum compound is preferably a molybdenum dithiocarbamate of the formula :

where R _j , R ₂ , R3 and R4 each independently represent a hydrogen atom, a C _j to C20 alkyl group, a Cg to C ₂ Q cycloalkyl, aryl, alkylaryl or aralkyl group, or a C3 to C ₂ n hydrocarbyl group containing an ester, ether, alcohol or carboxyl group; and X _j X ₂ , Y _j and Y each independently represent a sulphur or oxygen atom.

Examples of suitable groups for each of Rj, R ₂ , R3 and R4 include 2-ethylhexyl, nonylphenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, linoleyl, cyclohexyl and phenylmethyl. Preferably R _j to R4 are each Cg to C _jβ alkyl groups, more preferably CJQ to C14.

It is preferred that X _j and X ₂ are the same, and Y _j and Y ₂ are the same. Most preferably X _j and X ₂ are both sulphur atoms, and Yj and Y are both oxygen atoms.

Thus in a preferred embodiment the organo-molybdenum compound is sulphurised oxymolybdenum dithiocarbamate wherein the thiocarbamate groups contain CJQ to C24 alkyl groups. Such compounds are commercially available and are supplied, for example, by R.T. Vanderbilt Company.

Where the organo group of the organo-molybdenum compound is a carboxylate, this is

preferably a C _j to C50, more preferably a Cg to Cjg, carboxylate group. Examples of suitable carboxylates include octoate, e.g. 2-ethyl hexanoate, naphthenate and stearate. These compounds may be prepared, for example, by reacting molybdenum trioxide with the alkali metal salt of the appropriate carboxylic acid under suitable conditions.

Where the organo group of the organo-molybdenum compound is a xanthate, the compound preferably has the formula :

Mo ₂ (ROCS^ (II)

where R is a Cj to C30 hydrocarbyl group, preferably an alkyl group. Examples of suitable molybdenum xanthate compounds and their method of preparation are described in European patent application EP-A-433025, the disclosure of which is incorporated herein by reference.

The ashless organo-phosphorus compound is essentially free of metal, and preferably contains sulphur. Phosphorothiolothionates and phosphorothionates and mixtures thereof are preferred compounds

Phosphorothiolothionates have the general formula: S

II R5 O - P - SR7 (III)

0

Re

where R5, Rg and Rγ each independently represent a hydrocarbyl group which may be substituted with one or more functional groups or hetero atoms, or may be unsubstituted, and which may be branched or straight-chain.

Preferably R5 and Rg are each a Cj to C30 alkyl group, or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group. R7 is preferably a Cj to C30 alkyl group, a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group, or a C _j to C30 hydrocarbyl group containing one or more carboxylic acid, ester, alcohol, ether or amine groups, or an ammonium ion, preferably one or more carboxylic acid groups. Examples of suitable phosphorothiolothionates which are commercially available include VANLUBE 727, VANLUBE 7611 both supplied by R.T. Vanderbilt Company, IRGALUBE 63 supplied by Ciba-Geigy, and ECA 6330 supplied by Exxon Chemical Company.

Phosphorothionates have the general formula:

S II R ₈ 0 - P - 0 R ₁₀ (TV)

R ₉

where Rg, Rg, and RJQ each represent a hydrocarbyl group which may be substituted with one or more functional groups or hetero atoms, or may be unsubstituted, and which may be branched or straight-chain.

Preferably Rg and Rg are each a C _j to C30 alkyl group or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group. RJQ is preferably a Cj to C30 alkyl group or a Cg to C30 cycloalkyl, aryl, aralkyl or alkylaryl group, or a C _j to C30 hydrocarbyl group containing one or more amine, carboxylic acid, ester, alcohol or ether groups, or an ammonium ion, preferably an amine group or ammonium ion. Examples of suitable phosphorothionates which are commercially available include IRGALUBE TPPT supplied by Ciba-Geigy. Phosphorus thionates may also be obtained from the reaction of amines with dialkyldithiophosphoric acids.

The zinc thiophosphate compound (c) has the general formula :

where RJ J, Rj ₂ , R13 and R14 each independently represent a hydrogen atom, a C _j to C ₂ o alkyl group, a Cg to C g cycloalkyl, aryl, alkylaryl or aralkyl group, or a C3 to C ₂ Q hydrocarbyl group containing an ester, ether, alcohol or carboxyl group. Preferably each of RJJ to R14 is a C ₂ to Cjg, more preferably C3 to Cg, alkyl group which may be straight-chain or branched. Such compounds are commercially available and are supplied by, for example, Exxon Chemical Company.

The amounts of each of the antiwear additives (a) and (b) to be included in the lubricant composition according to the invention are the amounts that are effective in providing the desired level of antiwear performance, whilst reducing the amount of phosphorus to an acceptable level.

Whilst not being limited to any particular theory, it is believed that the antiwear properties of the organo-molybdenum compound (a) are generally attributable to the presence of the molybdenum. Thus when determining the amount of organo-molybdenum compound to be incorporated into the lubricant composition, one first needs to determine the desired amount of molybdenum. Preferably the amount of molybdenum contained in the lubricant composition is from 0.001 to 0.5 wt.%, more preferably 0.005 to 0.2 wt.%, and most preferably 0.01 to 0.05 wt.%, based on the total weight of the lubricant composition. The amount of organo-molybdenum compound that this corresponds to depends upon the type of compound selected.

Where the organo-molybdenum compound is a dithiocarbamate, the amount of compound used depends on the molecular weight of the R groups contained in the thiocarbamate groups, as defined in formula (I) above. Typically, however, the amount of molybdenum dithiocarbamate used is preferably from 0.01 to 3.0 wt.%, more preferably from 0.02 to 2.0 wt.%, and most preferably from 0.05 to 1.0 wt.%, based on the total weight of the lubricant composition.

Where the organo-molybdenum compound is a carboxylate, the amount of compound used depends upon the molecular weight of the carboxylate group selected. For example, where the carboxylate is 2-ethyl hexanoate, the amount of molybdenum carboxylate used is preferably from 0.005 to 2.5 wt.%, more preferably from 0.025 to 1.0 wt.%, and most preferably from 0.05 to 0.25 wt.%, based on the total weight of the lubricant composition.

Where the organo-molybdenum compound is a xanthate, the amount of compound used depends upon the molecular weight of the hydrocarbyl, e.g. alkyl, groups contained in the xanthate groups. Typically, however, the amount of molybdenum xanthate used is preferably from 0.003 to 2.0 wt.%, more preferably from 0.01 to 0.7 wt.% and most preferably from 0.03 to 0.2 wt.%, based on the total weight of the lubricant composition.

Similarly, it is believed that the antiwear properties of the ashless organo-phosphorus compound (b) and the zinc thiophosphate, when used, are generally attributable to the presence of the phosphorus. Thus, when determining the amounts of these compounds to incorporate, one first needs to determine the desired amount of phosphorus in the lubricant composition. Preferably the total amount of phosphorus contained in the lubricant composition is from 0.001 to 0.3 wt.%, more preferably from 0.01 to 0.2 wt.%, and most preferably from 0.02 to 0.1 wt.%, based on the total weight of the lubricant composition.

The amount of ashless organo-phosphorus compound and zinc thiophosphate compound (when used) that this corresponds to depends on the relative proportions of these compounds and the molecular weights of the particular compounds selected. Typically, however, the

amount of ashless organo-phosphorus compound incorporated into the lubricant composition is preferably from 0.01 to 3.0 wt.%, more preferably from 0.1 to 2.0 wt.%, and most preferably from 0.2 to 1.0 wt.%, based on the total weight of the lubricant composition, and the amount of zinc thiophosphate compound is preferably from 0.01 to 3.0 wt, more preferably 0.1 to 2.0 wt.%, and most preferably 0.2 to 1.0 wt.% based on the total weight of the lubricant composition.

The ratio of organo-molybdenum compound (a) to ashless organo-phosphorus compound (b) is preferably such that the weight ratio of molybdenum to phosphorus in the lubricant composition, due to the presence of compounds (a) and (b), is from 1:50 to 100:1, more preferably from 1:10 to 20:1, and most preferably from 1:1 to 10:1. The weight ratio of phosphorus derived from the ashless organo-phosphorus compound (b) to zinc thiophosphate compound (c) (when used) is preferably from 10:1 to 1:20, more preferably from 5:1 to 1:15 and most preferably 1:1 to 1:10.

The base oil employed in the lubricant composition according to the invention may be any base oil having a viscosity suitable for use of the lubricant in an engine e.g. as a crankcase oil or gear oil. Thus the base oil may be, for example, a conventionally refined mineral oil, an oil derived from coal tar or shale, a vegetable oil, an animal oil, a hydrocracked oil, or a synthetic oil, or a mixture of two or more of these types of oils. Examples of synthetic oils include hydroisomerised paraffins, polyalphaolefins, polybutene, alkylbenzenes, polyglycols, esters such as polyol esters or dibasic carboxylic acid esters, alkylene oxide polymers, and silicone oils. The viscosity of the base oil depends upon the intended use, but generally is in the range of from 3 to 26 cSt (mm ² /s)at 100°C, preferably from 3 to 20 cSt (mm ² /s)at 100°C.

The antiwear additive compounds (a) and (b), and (c) when used, may be mixed directly with the base oil, but, for ease of handling and introduction of the compounds to the base oil, are preferably in the form of additive concentrate comprising the additive compound, or mixture of both compounds, contained in a carrier fluid. The carrier fluid is typically an oil and may be, for example, any of the oils mentioned above in the description of the base oil. Alternatively, it may be an organic solvent, for example naphtha, benzene, toluene, xylene and the like. The carrier fluid should be compatible with the base oil of the lubricant composition, but otherwise is preferably inert. Generally the concentrate will comprise from 10 to 90 wt.% of the additive(s), preferably from 30 to 70 wt.%, the balance being the carrier fluid.

The lubricant composition according to the invention may also contain other additives, which may be added directly to the base oil, as a separate additive concentrate, or included in the concentrate of the antiwear additives. For example, where the lubricant is an engine oil, other additives that may be incorporated include one or more of a detergent, dispersant, antioxidant, corrosion inhibitor, extreme pressure agent, antifoaming agent, pour point

depressant and viscosity index improver. Such additives are well-known and the selection of appropriate additives could readily be determined by a person skilled in the art of lubricant formulating.

The lubricant composition may find use in any application where the parts to be lubricated are subject to wear. It is especially suitable for use as an engine oil for internal combustion engines.

The invention is illustrated by the following Examples.

Examples 1 to 3

A number of engine oils were formulated by blending an organo-molybdenum compound and an ashless organo-phosphorus compound with a conventional engine oil formulation (the "basecase" oil) which was based on a conventionally refined mineral oil and contained standard engine oil additives except that ZDDP was omitted. For comparative purposes, further engine oils were formulated omitting one or more of the antiwear additives, and, in one example, ZDDP was added.

The formulations are listed in Table 1 below.

The organo-molybdenum compounds used were: (i) MOLYVAN 822 (trade name) a molybdenum dithiocarbamate supplied by R.T. Vanderbilt Company, (ii) MOLYNAPALL (trade name), a molybdenum naphthenate supplied by Mooney Chemicals, and (iii) MOLYHEXCEM (trade name), molybdenum 2-ethyl hexanoate supplied by Mooney Chemicals. The molybdenum content of each of these compounds was determined using ICP (inductively-coupled plasma) analysis.

The ashless organo-phosphorus compounds used were: (i) IRGALUBE TPPT (trade name), a phosphorothionate supplied by Ciba-Geigy, (ii) VANLUBE 727 (trade name), a phosphorothiolothionate supplied by R.T. Vanderbilt Company, and (iii) "Amine DDP", an amine derivative of a phosphorothionate obtained by reacting the amine PRIMENE JMT (trade name) supplied by Rohm and Haas with dioctyldithiophosphoric acid. The phosphorus content of each of these compounds was determined using X-ray fluorescent analysis according to standard test AMS 86.002.

The ZDDP compound used was PARANOX 14 supplied by Exxon Chemical Company. The phosphorus content of this compound was also determined using the above X-ray fluorescent analysis technique.

The resulting engine oils were tested for valve train wear by measuring camshaft wear and tappet scuffing using a motored cylinder head test rig which is equivalent to the industry standard TU-3 engine test CEC L-38-T-87, which test procedure is available from the CEC Secretariat, 61 New Cavendish Street, London Wl 8AB.

The results are given in Table 1 below. All percentages are by weight based on the weight of the fully formulated engine oil.

In Table 1 the following abbreviations are used:

PN 14 = PARANOX 14

MV 822 = MOLYVAN 822

M.N.ALL = MOLYNAPALL

M.H.CEM = MOLYHEXCEM

I.TPPT = IRGALUBE TPPT

VL 727 = VANLUBE 727

P. JMT = PRIMENE JMT reacted with dioctyldithiophosphoric acid

Good results are indicated by a low value for camshaft wear and a high value for tappet scuffing. From the results it can be seen that addition of an organo-molybdenum compound as the sole antiwear additive produces only a small improvement in camshaft wear and some improvement in tappet scuffing over the basecase oil containing no antiwear additive. Likewise addition of solely an organo-phosphorus compound produces some improvement in camshaft wear and tappet scuffing. However addition of both compounds produces significant antiwear improvement. Furthermore the improvement achieved is greater than that achieved using ZDDP, even when the total active ingredient is higher for the ZDDP-containing formulation (Example 1A) than the formulation according to the invention (Example ID). Furthermore, better results than with ZDDP alone were achieved when the organo-molybdenum compound was 2-ethyl hexanoate (Example 3E) the results being only marginally less than with dithiocarbamate (Example 3C) and was achieved using only 0.07 wt.% of the additive compound as against 0.2 wt.% in the case of dithiocarbamate.

TABLE 1

Example Invention/ Basecase ZDDP Organo- Organo-P % Mo % P % Total Camshaft Tappet Comparison Oil Mo Active Wear (μm) Scuffing

Ingredient (Merit)

1A C I 1.2% - - - 0.1 0.1 7.25 4.5 PN 14

IB C I 0.2% - 0.01 - 0.01 11.12 5.0

CO MV 822

C 1C C I - 0.56% - 0.05 0.05 6.25 5.6

DO I.TPPT to H ID I I 0.2% 0.56% 0.01 0.05 0.06 4.0 7.9

H MV 822 I.TPPT

C 2A C II - - - - - 36.9 5.0

H m t 2B C II 1.0% 0.05 0.05 32.6 5.6 Z MV 822 m m

H 2C C II - 0.5% - 0.03 0.03 9.25 5.3

30 VL 727

C 2D I II 0.2% 0.5% 0.01 0.03 0.04 4.1 7.7 r- m MV 822 VL 727 is.* 3A C III 0.2% - 0.01 - 0.01 23.6 5.0 MV 822

3B C III - 1.19% - 0.05 0.05 13.13 6.9 P.JMT

3C I III 0.2% 1.19% 0.01 0.05 0.06 4.38 7.9 MV 822 P.JMT

3D I III 0.17% 1.19% 0.01 0.05 0.06 8.38 7.2 M.N.ALL P.JMT

3E I III 0.07% 1.19% 0.01 0.05 0.06 6.75 7.5 M.H.CEM P.JMT

Example 4

An engine oil was formulated by adding the following antiwear additives to a basecase oil consisting of conventional engine oil based on a conventionally refined mineral oil and containing standard engine oil additives other than ZDDP:

(a) 0.2 wt.% MOLYVAN 822 (molybdenum dithiocarbamate as in Example 1)

(b) 0.8 wt.% ECA 6330, a phosphorothiolothionate supplied by Exxon Chemical Company, and

(c) 1.0 wt.% PARANOX 14 (ZDDP as in Example 1)

The amount of molybdenum contained in (a) was determined using ICP (inductively- coupled plasma) analysis. The amount of phosphorus contained in each of (b) and (c) was determined using X-ray fluorescent analysis according to standard test AMS 86.002.

Comparative engine oils were formulated using the same basecase oil and omitting one or more of the above antiwear additives (a), (b) and (c).

The resulting engine oils were tested for valve train wear by measuring tappet wear according to the standard industry engine test VW 5106 Cam and Tappet Test (procedure P-VW 5106), which test procedure is available from VW AG, Postfach 3180, Wolfsburg 1, Germany

The resulting engine oils were tested for valve train wear by measuring tappet wear according to the standard industry engine test VW 5106 Cam and Tappet Rig.

The results are given in Table 2 below. All percentages are by weight based on the weight of the fully formulated engine oil.

TABLE 2

Example Organo-Mo Ashless-P ZDDP % Mo % P %Total Max. Tappet active wear (μm) ingredient

4A 0.2% 0.8% 1.0% 0.01 0.10 0.11 100

4B - - 1.2% - 0.10 0.10 123

4C 0.2% - 1.0% 0.01 0.09 0.10 127

4D - 0.8% 1.0% - 0.10 0.10 123

The lower the tappet wear value the better the antiwear performance of the lubricant. Thus the results show that for the same level of total phosphorus a significant improvement in antiwear performance is achieved when the antiwear agent is a combination of organo- molybdenum compound, ashless organo-phosphorus compound and ZDDP.