US2976238A

US2976238A - Oil-based compositions

Info

Publication number: US2976238A
Application number: US703753A
Authority: US
Inventors: Elliott John Scotchford; Edwards Eric Descamp
Original assignee: Castrol Ltd
Current assignee: Castrol Ltd
Priority date: 1956-12-24
Filing date: 1957-12-19
Publication date: 1961-03-21
Anticipated expiration: 1978-03-21
Also published as: NL103587C

Description

United .1: tes

OIL-BASED COMPOSITIONS John Scotchford Elliott and Eric Descamp Edwards, London, England, assignors to Castrol Limited, a British company No Drawing. Filed Dec. 19, 1957, Ser. No. 703,753

Claims priority, application Great Britain Dec. 24, 1956 8 Claims. (Cl. 252-325) This invention is for improvements in or relating to oil-based compositions and is particularly concerned with lubricating compositions.

It is an object of the present invention to provide lubricating compositions containing additives which additives have a high alkaline reserve combined with a relatively low ash content, said lubricating compositions being suitable for use in internal combustion engines.

A further object of the present invention is to provide oil-based compositions having anti-corrosive properties.

It is a still further object of the present invention to provide an improved lubricant for the cylinders of marine diesel engines burning boiler fuel or other fuel of high sulphur content.

In our British patent application No. 8,823/55 we have described and claimed a cylinder lubricant for marine diesel engines operating on boiler fuel or other fuel of high sulphur content, which lubricant comprises a mineral lubricating oil having incorporated therein an oilsoluble organic nonaromatic amine having not less than 7 carbon atoms or an oil-soluble non-aromatic amine salt of a weak acid, said organic non-aromatic amine or amine salt being present in an amount sufficient to provide at least of amine in the oil. The non-aromatic amines of this application effectively reduce cylinder Wear and improve piston cleanliness of marine diesels operating on boiler fuel, but they suffer from certain disadvantages in that they possess strong odours and have a caustic action on the skin, are prone to cause the removal of paint from surfaces with which they come into contact, and tend to react with carbon dioxide in the atmosphere with the consequent formation of oil-insoluble carbonates or carbamates which form an undesirable skin on the surface. Of the amine salts, on the other hand, those which have adequate oil-solubility, while free from these objections, have rather low neutralisation equivalents which necessitate their use in inconveniently large amounts.

The compositions of the present invention, on the other hand, incorporate oil-soluble compounds of mild odour which compounds are substantially neutral in reaction, yet they have higher neutralisation equivalents and can therefore be used in smaller amounts.

In internal combustion engine oils operating on more conventional fuels, one particular problem in engines operating in cold weather is the so-called cold sludging which is due to the ingress of water and fuel combustion products giving rise to the formation of a stiff emulsion or sludge. Under these conditions of operation, a serious accompaniment of cold sludging is the corrosion Patented Mar. 21, 1961 of piston rings and cylinder liners due to the presence of water and acidic products from the combustion of the fuel. The compositions of the present invention em ployed alone or having incorporated therein conventional detergent and antioxidant additives serve to retard the corrosion of piston rings and cylinder liners under these conditions.

The compositions of the present invention may be employed as lubricants for small two-stroke engines. While conventional mineral lubricating oils may be used for this purpose, the presence of additives to improve piston cleanliness and disperse or soften carbon deposits is often desirable.

The oil-based compositions of the present invention may also be used as storage oils, slushing compositions and general rust-preventing compositions such compositions including, if desired, conventional additives such as metal petroleum (mahogany) sulphonates, wool grease and the like.

Certain of the compositions of the present invention may also be employed as lubricants for steam turbines, such lubricants possessing good rust-preventive properties in the presence of water or salt water; conventional antioxidants will also generally be present in such compositions.

According to the present invention there is provided an oil-based composition comprising a mineral or synthetic oil having incorporated therein a proportion of a compound having the general formula wherein M is a polyvalent metal capable of forming ammino co-ordination complexes, A is the residue of an organic acid, B is an organic dior poly-amine, x and y are small integers satisfying the valency of M and A, z is a small integer such that the co-ordination number of M is partially or completely satisfied, and A and B are selected so that the compound is soluble in the oil.

The radical A has preferably one of the following where R and R are alkly, cycloalkyl, aralkyl, alkaryl or aryl groupings, and may carry substituents such as hydroxyl or ester groups or halogen atoms.

The metal M must be a metal capable of forming relatively stable ammino co-ordination complexes, and is desirably also a metal which is not prone to increase the oxidation rate of the oil in which it is dissolved. The preferred metals are zinc, cadmium, cobalt, tin, lead, nickel and chromium, although others, such as copper, iron (ferrous), mercury, silver, manganese and the rare or comparatively rare elements of group VIII of the periodic table, e.g. platinum, palladium, ruthenium, osmium or iridium, may be used if desired.

The complex amino compounds employed as the additives in the present invention may be prepared by reacting a salt M A with the organic dior poly-amine.

Examples of suitable salts M A, are the acetates,

ctoates, laurates, oleates, naphthenates, benzoates, alicylates, petroleum sulphonates, alklated aryl sulhonates and long chain alkyl and alkylated aryl hosphates.

Examples of the di or poly-amines B are ethylene dimine, diethylene triamine, triethylene tetramine, tetrathylene pentamine, mixtures of higher polyethylene olyamines, piperazine, p-phenylene diamine and various ommercially available long-chain diamines of the genral formula R"--NHCH CH CH NH wherein R rep- :sents an alkyl group derived from a fatty acid, e.g. iuric acid or from mixed fatty acids obtained from oconut oil, soya bean oil or tallow, these diamines being Jld under the registered trademark Duomeen.

If desired, heterocyclic dior poly-amines may be emloyed, examples of suitable compounds being. sold uner the trademark Bitran.

It is to be understood that in order-to produce oilluble compounds it is necessary to select the amine sed with reference to the nature of the metal salt with 'hich it is completed. If, for example, a metal petrolem sulphonate or a naphthenate is used, a wide range of ior poly-amines may be complexed therewith. If, on 1e other hand, a salt of a short chain organic acid, e .g. cetic acid, is used, it will be necessary to select a relavely long-chain amine, such as one of the Duomeens, 1 order to produce an oil-soluble complex compound. When the complex ammino compounds are intended I be employed as additives for lubricating oils which re to be subjected to relatively high temperatures, it is ecessary to select compounds derived from long-chain ior poly-amines, since compounds derived, for exmple, from the polyethylene polyamines tend to decomose with the formation of resinous substances which :nd to form objectionable gums on pistons, etc. Thus hen, for example, the complex compounds are to be nployed in lubricating compositions for 1.0. engine oils is desirable to select those derived from the )uomeens or other long-chain dior poly-amines.

The complex ammino compounds may be prepared by my means known to the art. Thus those made from il-soluble metal soaps or salts may conveniently be repared in solution, e.g. in mineral oil, by simply warmg with the dior poly-amine in the appropriate proporans, Generally the molar ratio of amine to metal salt ill not exceed 1:1, and it is often advantageous tohave l Ilid oil-insoluble metal salts, a convenient method is i reflux a solution of the dior poly-amine in petroleum her or benzene with a slight excess of the salt until the tter passes into solution, after which the solution is tered and the solvent removed by distillation. Comex compounds of this type are in general readily solue in hot mineral oil but tend to separate to some exnt on cooling. More useful mixed complexes can be 'epared by further reacting the oil-insoluble metal lt/amine complex with a proportion of an oil-soluble etal salt in such amounts that the molar ratio of total etal salts to the dior poly-amine is at least l:0.8.

Specific examples of the oil-soluble complex ammino umpounds of the present invention are:

nc naphthenate/diethylene triamine complex (1:0.8 molar ratio) nc acetate/Duomeen C complex nc naphthenate/Duomeen C complex nc naphthenate/Bitran P complex nc oleate/Duomeen C complex :ad naphthenate/Duomeen C complex :ad naphthenate/triethylene tetramine complex nc naphthenate/p-phenylene diamine complex Nickel petroleum sulphonate/Duomccn C complex Cadmium octyl phosphate/Duomeen C complex In one form of the present invention the complex ammino compound is of the type described in British patent application No. 39,206/56. Specific examples of complex compounds of this type are:

Zinc petroleum sulphonate/triethylene tetramine complex Zinc petroleum sulphonate/tetraethylene pentamine complex Tin petroleum sulphonate/triethylene tetramine complex Alternatively, complex compounds may be prepared from certain commercially available materials having a relatively high organic acidity, e.g. crude wool grease. These may be neutralised directly with a suitable metal oxide or hydroxide, e.g. zinc oxide, and then complexed with the desired amine.

It is to be understood that the foregoing examples are merely illustrative of the complex compounds which may be employed and are in no wise to be regarded as limiting the scope of the invention. The following me marks may, however, serve to indicate the scope and limitations of different sub-classes of the complex compounds intended for use in the compositions of the present invention.

The most generally useful complex compounds are those prepared from freely oil-soluble metal salts e.g. the laurates, oleates and, particularly, the naphthenates of metals such as zinc, nickel, cobalt, tin and chromium and long-chain diamines, particularly the Duomeens. As already indicated, the Duomeens" have the general formula R"-NHCH CH CH NH the radical R" being derived from a fatty acid, and substances are commercially available in which R" is derived from coconut fatty acids (Duomeen C), soya fatty acids (Duomeen S) and tallow fatty acids (Duomeen T). Any of these substances may be employed in the production of the complex compounds, but it is generally preferred to use Duomeen C as this substance has the best oilsolubility and the highest neutralisation equivalent. Zinc is generally the preferred metal both for economic reasons and because the zinc salts of organic acids can readily be prepared by direct neutralisation of the acids with zinc oxide in the presence of a little water. To obtain the maximum oil-solubility, particularly at low temperatures, it is generally desirable to have a small excess jofthe metal salt present, a molar ratio of saltzamine'of 1:0.8 being particularly suitable. Complex compounds of this general type are suitable for use in a variety of lubricating compositions in accordance with the present invention. Thus quite large amounts, up to about 30% by weight, may be used in cylinder oils for marine diesel engines burning boiler fuel, while quite small amounts e.g. 0.2% or less, are effective corrosion inhibitors when used in steam turbine oils, and they do not increase to an unacceptable degree the demulsification values of such oils.

Complex compounds having adequate oil-solubility may also be prepared from freely oil-soluble metal salts, e.g. zinc naphthenate, and diethylene triamine or other polyethylene polyamines. These may be used equally well'as corrosion inhibitors in steam turbine oils, but as already indicated their use should not be considered in lubricants liable to be subjected to relatively high temperatures.

Complex compounds prepared from metal petroleumoils is therefore contra-indicated. These compounds, like those derived from the metal salts of organic phosphoric acids, possess a lower reserve alkalinity than those derived from metal carboxylates because the organic sulphonic and phosphoric acids are strong acids not readily displaced from combination with the metal.

Complex compounds prepared from aromatic or heterocyclic dior poly-amines such as p-phenylene diamine and the Bitrans are in general less satisfactory as corrosion inhibitors than the classes already described.

The additives of the present invention may be employed, if desired, in conjunction with other additives commonly used in lubricating oils. Thus, for example, in oils for internal combustion engines there may be present conventional detergents such as metal petroleum (mahogany) sulphonates, and antioxidants such as zinc dialkyl dithiophosphates, metal alkyl phenol sulphides or phosphorised sulphurised terpenes.

The additives may be employed not only in mineral lubricating oils but also in synthetic oils, e.g. the dicarboxylic acid diester type and the polyglycol ether type of synthetic lubricant.

When the oil-based compositions of the present invention are employed as lubricants for the cylinders of marine diesel engines operating on boiler fuel or other fuel of high sulphur content they may contain from 2 percent to 20 percent by weight of the complex ammino compound. For use in the lubrication of internal combustion engines using more conventional fuels the additive is preferably used in a proportion of from 0.5 to 2 percent.

For use in turbine oils, selected additives may be used in concentrations ranging from 0.02% to 2.0% and preferably from 0.05% to 0.2%. In general rust-preventive compositions the additives may be employed in widely differing amounts depending on the application which is in mind; thus from about 0.1% up to or even 20% may be used depending on the severity of the conditions.

The following examples illustrate the preparation and properies of the complex compounds which may be used in the lubricating compositions of the present invention:

EXAMPLE 1 Zinc naphthenate diethylene triamine complex (Compound A) To 709 grams (0.55 mol) of an approximately 50% solution of zinc naphthenate in mineral oil were added 51.5 grams (0.5 mol) of diethylene triamine. An exothermic reaction took place, following which the material was stirred at 110 C. for minutes. The product was a brown oil containing 4.8% zinc and 2.7% nitrogen, and was freely soluble in mineral oil although diethylene triamine itself was quite insoluble.

The reserve alkalinity of this complex compond was found to be 176 mgs. KOH per gram, the reserve alkalinity of the original zinc naphthenate concentrate being about 80 mgs. KOH per gram.

Reserve alkalinity was determined by refluxing a weighed quantity of the sample with a known excess of 0.1 N HQ in a solution consisting of 5% methanol 45% ethanol 50% water and back-titrating with 0.1 N NaOH using screened methyl orange as indicator.

EXAMPLE 2 Zinc naphthenate "Duomeen C complex (Compound B) A mixture of 1911 grams (1.5 mols) of an approximately 50% solution of zinc naphthenate in mineral oil and 300 grams (1.2 mols) of Duomeen C" were heated to 120 C. and stirred for a few minutes until a bright clear product was obtained.

The product was freely miscible with mineral oil although the oil-solubility of Duomeen C itself was very limited. It contained 4.3% zinc and had a reserve alkalinity" of about 110.

EXAMPLE 3 Zinc acetate Duomeen C" complex To a solution of 32.1 grams (0.13 mol) of Duomeen C 'dissolved in 200 mls. of toluene were added"18.35 7.

grams (0.10 mol) of anhydrous zinc acetate and the mixture was refluxed until virtually all the zinc acetate had passed into solution. After filtering from a little solid matter, the toluene was removed by distillation in vacuo.

The product contained 13.6% zinc and had a reserve alkalinity of about 550 mgs. KOH per gm. It was readily soluble in hot mineral oil but some separation occurred on cooling.

EXAMPLE 4 Zinc acetate-naphthenate Duomeen C complex (1:0.5:1 molar ratio) A mixture of 18.35 gms. (0.1 mol) of anhydrous Zinc acetate and 25.0 gms. (0.1 mol) of Duomeen C were stirred together in a beaker and heated slowly to 130 C. Most of the zinc acetate appeared to react in the temperature range to C. yielding a butt opaque viscous liquid. 53.6 grams (0.05 mol) of an approximately 50% oil solution of zinc naphthenate was now added and heating and stirring continued for a few minutes. The zinc naphthenate employed contained 12% zinc. The product was mixed with filter-aid and filtered hot. On dilution with an equal weight of mineral oil a clear stable 36% oil concentrate was obtained containing 5.2% of zinc and having a reserve alkalinity of about mgs. KOH per gram.

EXAMPLE 5 Zinc salt of crude wool grease Duomeen C" complex (Compound C) To 256 gms. (0.2 mol) of a crude wool grease, containing free acidity corresponding to an equivalent weight of 1278, was added 10 gms. of zinc oxide made into a paste with water. The mixture was thoroughly stirred at 90 C. until the zinc oxide had largely reacted, after which the product was heated to C. to remove water.

To 100 gms. (0.038 mol) of this product, held at 90 C., were added 7.9 gms. (0.032 mol) of Duomeen C. An exothermic reaction took place and the mixture was then heated with stirring until the temperature reached 120 C.

The product was a dark brown solid containing 3.04%

zinc.

By the general procedure outlined above, a large number of complex compounds suitable for use in the oilbased compositions of the present invention, may be prepared. The direct heating method of Examples 1 and 2 is generally the preferred method, but various compounds derived from oil-insoluble metal salts, e.g. zinc benzoate, zinc salicylate, may be made by the method of Example 3.

Details of those compounds used in the tests which follow are listed in Table I:

ap ease Where the composition of the dior poly-amine was at known with certainty, the amount to be complexed ith the metal salt was calculated from a determination Ethe basicity of the amine.

In order to demonstrate the anticorrosive properties certain of the oil-based compositions of the present .VBDIIOH, the additives were dissolved in a typical steam lrbine base oil consisting of approximately 80% by eight mineral oil A and 20% by weight mineral oil 3," and examined for effect on demulsification number 1d rust preventive characteristics in the presence of salt ater. The methods of test employed were those delribed in Standard Methods for Testing Petroleum and ;Products (16th Edition, February 1957), serial desigrtions I.P. 19/55 and LP. 135/56 respectively. The rellts of a series of tests are summarized in Table II.

TABLE II Percent Demulsifi- Results of 24 hours Test Additive by cation salt-water N 0. Weight Number corrosion test at in oil 140 F.

None 60 Severe rusting. Compound A 0. 2 180 N o rusting.

Compound B.-- 2.0 300 Do.

- do 0. 1 240 Do. Compound C. 0. 2 over 1200 Do. Compound D... 0.2 270 Do. Compound E.-- 0. 2 720 Do. Compound F.-- 0. 2 570 Do. Compound G--- 0. 2 390 Do. Compound H..- 1. 0 75 Moderate rusting.

Compound I 0. 2 150 Very slight rusting.

Compound .l 0.2 150 No rusting.

In mineral oil B (demulsification N o. 30).

Oil A was a mineral oil having a viscosity of about i seconds Redwood I at 140 F. and oil B was a lvent-refined oil of viscosity about 65 seconds Redwood it 140 F.

It will be seen that while many of the additives tested are eifective inhibitors of corrosion under the condims of this test, some, particularly compounds C and E, creased the demulsification number of the oil to an ldesirable extent and therefore were not suitable for e in turbine oils.

Representative oil-based compositions of the present vention were subjected to a very severe test applicable anticorrosive engine lubricating oils designed to pro- :t aero-engines from corrosion during storage and shipent overseas.

The test procedure is described in Ministry of Defence ecification DEF 2181, Appendix B (issued March 13, 53) and involved immersion of mild steel panels in a solution of hydrobromic acid in kerosine followed by immersion in the oil composition, diluted with petroleum ether, followed by draining and maintenance at 20 C.-' -2 C. for 24 hours in a glass vessel over saturated zinc sulphate solution. Protection against corrosion was considered adequate if the average weight gain of the test panels (tested in quadruplicate) did not exceed 5 mgs. Results of these tests are summarized in Table III.

TABLE III [All compositions were based on mineral oil" 0" Average 'l gest Additives Present, Percent by weight refit iss) 5% Compound B 13 4% Sodium petroleum sulphonate soln. (approx. 5.5

45% oil concentrate). 14 10% Compound 0 10.8 5% Compound 0 15 4% Sodium petroleum sulphonate soln. (approx. 4.8

45% oil concentrate). 16 10% Compound D 4.95

Mineral oil C was a conventionally refined paraffinic brightstock of viscosity about 600 seconds Redwood I at F.

It will be seen from the foregoing table that 10% of Compound D gave satisfactory protection against corrosion, but that 10% of Compound C was inadequate. Satisfactory protection could, however, be obtained by the use of mixtures of Compounds B or C with sodium petroleum sulphonates.

In order to assess the effectiveness of certain of the oil-based compositions of the present invention as cylinder lubricants for marine diesel engines operating on boiler fuel, engine tests were carried out in a two-cylinder Lister engine (model 122, bore 4 /2", stroke 5 /2") modified for separate mechanical lubrication of one cylinder.

This engine was operated under the following condi= tions:

No. 1 cylinder was lubricated mechanically, the rate of feed of the test oil to this cylinder being 20 cc. per hour per lubricator Le. 40 cc. per hour total. No. 2

cylinder was lubricated normally with oil from the sump.

In the tests, details of which are tabulated in Table IV the base oil (mineral oil D) was used throughout in the sump while various lubricants prepared in accordance with the present invention were used for lubricating No. 1 cylinder. Since these lubricants were all based on mineral oil D a direct measure of the efli'ectiveness of 4 the additives could be obtained in any one test by comparing the wear of the two cylinders and cleanliness of the two pistons.

Mineral oil D was a solvent-refined mineral oil of viscosity approximately seconds Redwood l at 140 F.

TABLE IV.-LISTER ENGINE TESTS Piston Rating Test 'lop Total Test Lubricant Composition (Cylinder No. 1) duration Cylinder ring ring No. (hours) No. wt. wt. Ring loss loss Skirt Lands groove (mgs) (mgs.) lacquer M a a a; :19 2 93.5% Mineral OilD 5.0% Basic barium petroleum sulphonate soln. 1 174 310 29. 5 6.9 18 (approx. 45% in mineral oil) 44 2 172 317 29.0 7.3

1.5% Zinc dihexyl dithiophosphate soln. (approx.

50% in mineral oil) 91% Mineral Oil D. 19 8% Compound B 96 1 73 161 30. 0 9. 9 7. 6 1% Basic barium petroleum sulphonate soln. (ap- 2 290 522 26.3 3.2 0

prox. 45% in mineral oil) 2o As test No.19 100 l at 23:2 2:3 3:3

Maximum rating for piston skir 30.0 Maximum rating for piston lands. 10.0 Maximum rating for ring groove lacquer- 10. 0

These maximum figures were arbitrary ratings signifying that the parts concerned were perfectly clean. A minimum ratin of 0 would be given for a completely black piston or for lands or grooves completely coated with black lacquer.

It will be seen from the foregoing table that although some variation in piston ring weight loss was experienced using the same base oil in different tests, a typical composition of the present invention (tests Nos. 19 and 20) produced a very substantial reduction in wear as compared with the base oil, this being coupled with a marked increase in piston cleanliness. When both cylinders were lubricated with the base oil (test No. 17) there was no significant difference between the two pistons. When a conventional heavy duty oil containing additives in Supplement 1 proportions was used (test No. 18) it showed no noticeable improvement over the base oil.

A further series of tests were carried out in a Petter AV-l engine operating under the following conditions:

The fuel used was the same as that used in the Lister piston ring gurnming, for the reason already stated. It will be observed that the composition containing 25% Compound B (test No. 24) gave both an exceptionally clean piston and very low ring loss. This composition contained, in fact, only about 14% of the actual additive, since Compound B was a oil concentrate.

In contrast with prior art marine diesel cylinder lubricants containing oil-soluble amines, the compositions of the present invention have only a mild odour, are without caustic action on the skin and do not remove paint. Furthermore, they are stable on storage over long periods and do not react with carbon dioxide in the atmosphere. They are also without significant action on metals such as copper, brass, Phosphor bronze, zinc and aluminium at the temperatures encountered in service.

We claim:

1. An oil-based composition consisting essentially of a lubricating oil having incorporated therein from 2% to 30% by weight of an oil-soluble complex ammino compound having the general formula M A B wherein M is selected from the group consisting of zinc, cadmium, cobalt, tin, lead, nickel and chromium; A is selected from the group consisting of engine tests. Results of the tests are summarized in R.0 o 0- R.SOz- RO-P-0- Table V. 0

TABLE V.-PETTER ENGINE TESTS Test No 21 22 23 24 91% Oil D 74% Oil D. 907 on D I? fi i BM l 8 0 as c ariumpel as c arium e- Lubflwm Composition on 10% Compound A i roleum sulphogroleum sulphonate soln. (approx. nate soln. (approx. 45% in Oil). 45% in oil).

Maximum ratmg Test Result obtainable Crown cutting rating 5. 0 3. 9 3. 6 4. 1 3.9 10. 0 4. 1 3. 7 5. 1 5. 2 10.0 9.0 7. 5 10.0 10.0 10. 0 0. 6 0. 0 5. 3 9. 7 30. 0 22. 3 28. 2 29. 2 30. O 35. 0 28. O 11. 7 35. 0 35. 0 10. 0 O. 9 0. 0 5. 1 3. 1 892 459 419 261 1, 475 745 623 464 l Relates to combined weight loss of 5 rings except in Test No. 22 where only 4 rings were used. It will be seen from this table that typical compositions and of the present invention (tests Nos. 22 to 24) effected a substantial reduction in piston ring corrosion as com- ;fi0 pared with the plain mineral oil (test No. 21). Com- 0 positions containing Compound B, however, were much superior to that containing compound A with respect to where R and R are selected from the group consisting hat the coordination number of M is at least partially.

atisfied. p

2. A composition as claimed in claim 1 herein the ubricating oil is a mineral oil. r t

3. A composition as claimed in claim 1 wherein the lbricating oil is selected from the'groupconsisting of icarboxylic acid diester oils and pblyglycolether oils.

4. A composition as claimed in claim 1 wherein the omplex ammino compound is a complex consisting of inc naphthenate/R"-NHCH CH CH NH wherein R" a an alkyl group having from 8 to l8 carbon atoms.

5. A composition as claimed in claim 1 wherein the omplex ammino compound is a complex consisting of inc oleate/R"NHCH CI I CH NH wherein R" is an lkyl group having from 8 to 18 atoms.

6. A composition as claimed in claim 1 wherein the omplex ammino compound is a complex consisting of :ad naphthenate/ "NHCH CH CH NH wherein R" i an alkyl group having from 8 to 18 carbon atoms.

7. A composition as claimed in claim 1 wherein there is present from 5 to 30 percent by weight of the oil-solu blecompleii ariimiribbmpound. 8.1'A' cylinder lubricant for'marinfdieselsoperating on fuel :Qf high sulphur coiatent'consisting essentially of a mineral oilhaying incorporated therein; romZ to 3Q percent by weight of an 'oil-soluble'complex amminocompound consisting of I 4 zinc naphthenatel 'fNl-IcH cH cH- NH having a molar ratio of metal salt to the diainine'of at least 1:0.8, wherein R is'an alkyl group having from 8 to 18 carbon atoms. 1

- References (Zited in the tile of this patent UNI ED sTATias PATENTS 2,684,292 Caron et al. July 20,1954 2,692,858 Evans et al. Oct; 26, 1954 2,696,473 Sokol Dec. 7,,1954 2,736,658 Pfohl et al. Feb. 28, 1956 2,737,492 Beegle et a1. 22---; Mar. 6,1956 2,752,311 McCoy et al. June 26, 1956 2,798,045 Buck et al. July), 195'! 2,805,996 Deger 4....-- Sept. -10, 1957 2,808,376 Lowe 'i. Oct. 1, 1957 H RE NPAIE 696,064-

Great Britain Ass-26,1953

mil

Claims

1. AN OIL-BASED COMPOSITION CONSISTING ESSENTIALLY OF A LUBRICATING OIL HAVING INCORPORATED THEREIN FROM 2% TO 30% BY WEILGHT OF AN OIL-SOLUBLE COMPLEX AMMINO COMPOUND HAVING THE GENERAL FORMULA MXAYB2, WHEREIN M IS SELECTED FROM THE GROUP CONSISTING OF ZINC, CADMIUM, COLBALT, TIN, LEAD, NICKEL AND CHROMIUM, A IS SELECTED FROM THE GROUP CONSISTING OF