US2420068A

US2420068A - Lubricant

Info

Publication number: US2420068A
Application number: US516704A
Authority: US
Inventors: Gordon W Duncan; John C Zimmer
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1944-01-01
Filing date: 1944-01-01
Publication date: 1947-05-06
Anticipated expiration: 1964-05-06

Description

2,420,068 carom Gordon W. Duncam-Westfleld, and .lohn cummmer, Union, N. 3., asslgnors to Standard Gil Development Company, a corporation of Dela- No Drawing. Application January 1, 19%, Serial No. 5165M The present invention relates to mineral lubricatinc oils, particularly those oils containing additives in the nature of detergents, rust preventives and extreme pressure agents. More par tlcularly, the invention is concerned with compounded mineral lubricating oils which are not subject to or will not show additive separation in the presence of water.

It is known that internal combustion engines, both of the Diesel type and of the spark ignition type, which are subject to long and continuous periods of use as, for example, in. long-haul trucking service, high-speed marine service, certain types of aeronautical service, etc., require special-lubricating oils commonly designated as heavy duty oils which are compounded especially iorthis type of service. Mineral lubricating oils which are not so expressly prepared deteriorate relatively rapidly in service, depositing sludge,

carbonaceous materials, or varnish-like coatings.

on such surfaces as cylinder walls, piston skirts, piston ringgrooves, etc, and creating an otherwise unclean condition within the engine. For the purpose of counteracting to as great an extent as possible the tendency of mineral lubricating oils to form these deposits, materials of a detergent nature are incorporated into mineral oils destined for heavy duty uses. Generally speaking, these additives are metallic derivatives of organic-compounds, but regardless of their exact chemical configuration, they all exhibit the property of reducing or preventing the deposition oi carbonaceous or gummy residues and varnish-like films resulting from the deterioration of the lubricating oil. The more common of the detergent additives present in heavy duty oils in amounts ranging from 0.5 to are such compounds as metal naphthenates, metal phenates, metal phenol sulfides, and polysulfides, reaction products of metal phenol sulfides with P235, metal carboxylates, metal sulfonates, metal alcoholates, metal salts of esters of acids or thio acids of phosphorus, etc. where the metal ion is a polyvalent metal ion, such as calcium, barium, tin, aluminum, zinc, magnesium, strontium, lithium,- nickel, etc. Certain nonmetallic organic compounds are also employed on occasion.

Detergent additives used for improving mineral lubricatingoils for heavy duty servic are often somewhat hvdrophiiic. and as .a result they reservoir.

tend to form emulsions in the presence of water and to drop out of the oil solution, which action results in a heavy duty oil of impaired efiectiveness. Normally, mineral lubricating oils used in internal combustion engines are not expected to come in contact with water. However, situations beyond the control of the oil refiner do arise where the prepared lubricating oil does come in contact with water and these occurrences present themselves with sumcient regularity that additive loss through contact with water becomes a serious problem. One instance where loss of additives through contact with water occurs is during shipment of the oil in large size drums or tank cars. Either through atmospheric condensation or leakage of rain water, or because, through oversight, it is left in the drum after cleaning, water is permitted to mix with the oil and precipitate out the detergent additive. Water may also come into contact with the oil in normal automotive operation, particularly during the winter, when low temperatures cause moisture to condense in the crankcase. Another instance where the deleterious action of water on compounded heavy duty oils has been noted is in connection with certain large Diesel installations where, after installation or after the engine has been given a general overhauling, the whole lubricating system including the oil reservoir is washed out with water and then flushed with some of the lubricant intended to be used for normal lubrication. After the flushing operation, the oil is centrifuged to dispose of the water and the oil is then put back into the oil If the additive in the oil is hydrophilic in nature, this method of removing water from the oil also removes some of the detergent additive .and thus the oil returned to the system is not of the quality desired for such use. It is obvious from the foregoing that some means of retaining detergent additives in the oil even in the presence of water would be very beneficial. The principal object of the present invention resides in the provision of a compounded lubricant for use in the capacity set forth which, when accidentally .or otherwise placed in contact or mixed with water, will not loseany substantial amount of the compounding agent. This and other objects to be attained by the use. of the present invention will be apparent to those skilled S. U. .S. at 100 3 in the art upon reading the following description.

It has now been discoveredthat compounded oils having dissolved therein appreciably hydroagainst emulsiiication and additive separation by the incorporation of aliphatic amines having from 8-22-carbon atoms to the molecule. Such compounded oils range in viscosity from 90-1000 F., with pour points usually from 25 to +10 F. and contain from 0.5 to of additives, such as metal sulfides, reaction products of metal phenol sulfldes with P285, metal carboxylates, metal suli'onates, metal naphthenates, metal alcoh'olates.

metal salts of the esters of acids or thio acids of phosphorus, etc., or mixtures of the foregoing additives. In general, the metal derivatives of organic compounds utilizable as detergent additives contain ions of polyvalent metals, specific examples of such metals being calcium, barium, aluminum, tin and zinc. The non-metallic detergent additives include materials such as the naturally occurring phosphatides. The usual meth'odof blending compounded oils is to use an oil concentrate of the additive which is dissolved may be stabilized phenates, metal phenol in the mineral oil in the required amount to give the desired product, which solution may be hastened by means of agitation and heat. The detergent additives are frequently made in situ in oil solution so that after removal of the byproducts of the reaction, an oil concentrate of the desired additive is obtained directly and this is then used later to make the finished oil by blending it with the proper amount of basestock.

According to the present invention, saturated and unsaturated aliphatic primary amines containing from 8-22 carbon atoms to the molecule will, when present in the compounded heavy duty oil in amounts ranging from 0.005 to 0.5% by" weight and preferably 0.01-0.3% by weight, reduce to negligible proportions the emulsification of the oil with water and the additive separation caused thereby. 0f the various saturated and unsaturated primary aliphatic amines applicable for the purposes of the present invention, octadecenyl amine (oleyl amine), which is commercially available as' a mixture of 50% octadecenyl amine, 25% octadecyl amine and 25% h'exadecyl amine, is preferred. Other suitable amines are octadecyl amine (stearyl amine), LoroP' amine (commercial cocoanut oil amine) and hexadecyl amine In general. amine derivatives 0: from animal and vegetable fat: are satisfactory for our purpose. The amine: may be blended into previously compounded oil: by means of heat suflicient to hasten solution If desired, the amines can be incorporated in the oil concentrates of additives at the time that the concentrates are prepared, in which case the amines will be incorporated in amounts ranging from 1.0 to 20% by weight based upon the weight of the detergent additive present in the oil concentrate, depending upon the concentration of amines desired in the final compounded oil. If desired, the stabilizing agent may be incorporated in concentrates of other additives, such. as antioxidants bearing corrosion inhibitors, film strength agents, thickeners, pour depressants, and the like. The various detergent additives differ somewhat in their reaction toward water and the amount of detergent additive present is also influential in determining the amount of amines required to efiectively reduce additive separation; however, the preferred range of 0.01- 0.3% by weight of amines will, in most instances, be found suflicient to give adequate protection against emulsiflcation and additive separation.

A preferred compounded lubricating oil illustrating the present invention is prepared according to the following formula:

(cetyl amine). the fatty acids Parts Mineral lubricating oil 100 Mixture of barium tertiary octyl phenol sulfide, calcium suifonate and the reaction product of barium tertiary octyl phenol sulfide with P285 0.5-5 Octadecenylamine 001-03 For the purpose of demonstrating the eflectiveness of aliphatic primary amines as emulsification preventives and stabilizers against additive separation, cc. of an S. A. E. 10 grade mineral lubricating oil containing detergent additives was shaken violently for 20 seconds with 50 cc."oi' distilled water in a cc. centrifuge tube and then centrifuged for 5 minutes at 1800 R. P. M. In this test, the separation of additive is indicated by a collar of heavy cream-like emulsion lying between the oil and water phases. The volume of the emulsion is an indication of the tendency of the detergent to separate as a result of water contamination and, conversely, of the effectiveness of-the stabilizing agent employed.

Table I Volume oi Blend Emulsion SAE' 10 Solvent Extracted Naphthmic Lube Oil 1. +1.6% calcium salt of white oil sulionic acids 8 cc.

2. l)+0.5% di-Z-ethyl bexylamine 7 cc,

3. 1 +0.57 di-2-ethyl hexyl amine ethanol 3 cc.

4. 51 +03%; phenyl ethanol amine (incompletely solubl 3 cc.

5. 1 +0.57 diamylnitrosoamine 3 cc.

6. l)+0.57 hepta dec 1 imidazoline- 1 cc.

7. l;+0.2 7 hexa decy amine N o emulsion.

8. 1 +03%? "Lox-o1 amine Trace emulsion. 9. 1 +0.27 octadecyl amine; No emulsion. l0. 1 +01%; octadecyl amine. o. 11. l +0.05% octadecyl amine... Trace emulsion. l2. l)+0.3% octadeceny1amine No emulsion. Biit? t ii i t t i"t iaiifia" 1 n a um er.o cy p eno e .1800. i5. (l4)+ 0.1% octadecylamine No emulsion. 16. Base oil plus 1.75% calcium sulionate, 1.0% P treated bari cc. 1?. (l6)+0.2% octadecyiamine No emulsion. l8. Basle OilgJlilS 1.5% calcium sulionate+ 5 barium tert. octylphenol sulfide+l.0% zinc tert. octylphenol sulfide thio- 7 cc.

p osp a e. 19. l8;+0.05 o octade lamina 3 cc. 20. 18 +0.1 0 octadecy amine No emulsion.

The above data clearly show that the agents of 11S invention, the long chain primary aliphatic mines, are very eiiective in counteracting addiive separation resulting from water contaminaion of compounded lubricants. It is also shown hat other amines, with the exception of heptavecyl imidazoline which is similar in general tructure to the long chain primary aliphatic mines. are of little effect in combating this pheiomenon.

In a test somewhat similar to the above, c. of compounded oil is shaken for 20 seconds vith 10 cc. of distilled water in a '25 cc. graduited cylinder and allowed to stand one-half hour. the following dataillustrate the effectiveness of mines of our preferred class over others:

7. Composition according to claim 1 in which the amine is octadecyl amine. 1

8. Composition according to claim 1 in which the amine is hexadecyl amine.

9. An improved lubricating oil composition consisting of a mineral lubricating oil containing from 05-23% of calcium sulfonate of mineral oilsoluble sulfonic acids and 0.01-0.3% of octadecenyl amine. v

10. An improved lubricating oil composition consisting of a mineral lubricating oil containing about 1.5% of calcium sulfonate of petroleum oil soluble sulfonic acids and 0.1% of octadecenyl amine.

11. An improved lubricating oil composition consisting of a mineral lubricating oil contain- Table II Blend Volume 0! Emulsion S11E10 Solvent E'flmcfed Naphi'henlc Labs 0!! +15% calcium sulionate (li+l7; diethylnrnin ethanol. (ii-P05 2. riicvciohexyiamine l. 2. 3. 'i. 5. 6. 7. li+0.l% Lornl" amine... 8. +05% ociarlecylarnine.. 9. (+0 octedecylamlne... 10. (+05% oeiariecenylamine ll. dbl-0.1% octnriecenyiamine Bas oil-i-l.0 barium tort. octyl phenol sulfide (12)+0.5% octsdecylaznine Oil guise completely emulsified.

. 2.5 cc. emulsion.

Oil phase completely emulsified. No emulsion.

o. 2 cc. emulsion.

0.5 cc. emulsion.

In still another test for the water sensitivity of lubricating oil additives, 600 grams of a solvent extracted Mid-Continent S. A. E. lubricating oil containing 1.5% oi? calcium sulfonate, 0.5% barium tertiary octyl phenol sulfide, and 1.0% of the zinc salt of tertiary octyl phenol sulfide thio phosphate was thoroughly agitated with 1% distilled water in a one liter beaker for one minute. After standing 24 hours, 14 cc. of an emulsion of additive, water. and oil had separated. On repeatine the test with the oil containing. in addition. 0.3% of Lorol amine. no emulsion or separation of additive was obtained. a

What is claimed is:

1. An improved lubricating oil composition consisting of a mineral lubricating oil containing from 0.5 to 5% of an oil-soluble hydronhilic polyvalent metal-containing derivative of an organic compound. said metal compound possessing engine deter ent properties, and from 0.01 to 0.3% of an aliphatic primary amine containing from 8 to 22 carbon atoms per molecule.

2. A composition according to claim 1 in which the metal-containing compound is an alkaline earth metal sulfonate.

3, A composition according toclaim 1 in which the metal-containing compound is an alkaline earth metal aikvlated phenol sulfide.

4. A composition according to claim 1 in which the metal-containing compound is an alkaline earth metal alkvlated phenol sulilde reacted with phosphorus sulfide.

5. A composition according to claim 1 in which the metal-containing compound is a mixture of an alkaline earth'rnetal sulronate and an alkaline earth metal alkylated phenol sulfide reacted with a sulfide of phosphorus.

'6. Composition according to claim 1 in which the amine is octadecenyl amine.

Ill

ing from 055% of barium tertiary octyl phenol sulfide and 0.01-0.3% of octadecenyl amine.

12. An improved lubricating oil composition consisting of a mineral lubricating oil containing 1% of barium tertiary octyl phenol sulfide and 0.1% of octadecenyl amine.

13. An improved lubricating oil composition consisting of a mineral lubricating oil containing about 1.75% calcium petroleum sulionate, about 1.0% of the reaction product of barium tertiary oct'ylphenol sulfide with P285, and 0.2% octadecylamine.

14. An improved lubricating oil composition consisting of a mineral lubricating oil containing about 1.5% calcium petroleum sulfonate, 0.5% barium tertiary octylphenol sulfide, about 1.0% zinc tertiary octylphenol sulfide thiophosphate, and about 0.1% octadecylamine.

oonnon w. DUNCAN, JOHN c.