US2503401A

US2503401A - Lubricants

Info

Publication number: US2503401A
Application number: US83757A
Authority: US
Inventors: Leonard A Mattano; Lawson W Mixon
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1949-03-26
Filing date: 1949-03-26
Publication date: 1950-04-11
Anticipated expiration: 1967-04-11

Description

- 1 a... Apr. 11, 1950 I UNITED STATES PATENT OFF! LUBRICANTS Leonard A. Mattano and Lawson W. mond, Ind., assignors to Standard liiixon, Ham- Oil Company,

Chicago, 111., a corporation of Indiana No Drawing. Application 7 Serial No. 83,7

March to, 1949, 57 p 11 Claims. (Cl. 252-483) The present invention relates ,to compositions possessing'corrosion and/or rust preventive properties. More particularly, the inventionrelates to oleaginous compositions which possess corrosion and/or rust inhibiting properties, particularly when such compositions are used in systems prevention or inhibition of such corrosion or rusting is highly important. Similar problems exist in the lubrication of certain types of marine engines.

The present invention is also applicable to anti-rust or slushing compositions for the protection of metals against corrosion and/or rusting. Metallic products, prior to storage, are coated with an anti-rust material to prevent corrosion and/or' rusting while'in storage. Similarly, fabricated metallic articles and finished or semi-finished metallic stocks destined for shipment by rail or by water or to be stored, are protected against attack by moisture by coating such materials with anti-rust or slushing compounds.

It is an object of the present invention to provide an improved composition which will effectively inhibit or prevent thecorrosion and/or rusting of metallic surfaces.

Another object of the invention is to provide an improved composition which will efiectively inhibit or prevent the rusting and/or corrosion of metallic surfaces of equipment which come in contact with water or steam.

A further object of the invention is to provide a slushing composition which will effectively inhibit or prevent the rusting and/or corrosion of metal surfaces.

Still another object of the invention is to pro- 'vide a lubricant composition which will efiectively inhibit or prevent the corrosion and/or rusting of metal surfaces of equipment employing such lubricant, particularly equipment in which water or steam may be present.

We have discovered that the foregoing objects can be attained by incorporating in organic compositions, particularly one containing a major proportion of an oleaginous material, such asa natural or synthetic hydrocarbon oil, a mineral oil, a vegetable, marine or animal oil, synthetic ester-type oils, or combinations thereof, a small amount, for example, from about 0.001% toabout 2%, and preferably from about 0.002% to about 0.1% by weight, of a 1,3,4-tricarboxy-2-thiabutane havin the general formula in which the substituents R, R and R" are selected from the group consisting of hydrogen and an alkyl radical, and in which at least one of the Rs is hydrogen and at least one of the Rs is an alky] radical. At least one of the alkyl radicals should contain at least 10 carbon atoms, and

.preferably from about 10 to about 16 carbon atoms.

Specific examples of compounds illustrative of compounds coming within the above general forinla are the following:

l-decylcarboxy-3,4-dicarboxy-2-thiabutane l-dodecylcarboxy-3,4-dicarboxyr2-thiabutane 1-tetradecylcarboxy-3,4-dicarboxy-2-thiabutane 1-cetylcarboxy-3,4-dicarboxy-2-thiabutane '1-octadecy1carboxy-3,4-dicarboxy-r2-thiabutane 4-tetradecylcarboxy-1,3-dicarboxy-2-thiabutane 3-cetylcarboxy-1,4-dicarboxy-2-thiabutane 3,4-di-dodecylcarboxy-l-carboxy-Z-thiabutane It is not intended to imply that all esters of the herein-described type serve with identical efllciency as anti-rust or anti-corrosion agents. While they are all effective they will exhibit some variation depending upon the nature and severity of the service to which they are subject, the nature of the metal to be protected, the relative solubility. of the ester in the media which may be used for application of the ester to the metal surface and the relative stability of the ester at the service temperature.

Members of the herein-described class of compounds can be readily prepared by neutralizing maleic acid with an alkali metal hydroxide, such as sodium hydroxide, and adding to the neutralized product an alcoholic solution of a thiogly- I aooaeor temperature until titration with iodine indicates that the addition is substantially complete. The product is then acidified, preferably with an aqueous solution of hydrochloric acid, the acidifled product extracted with a hydrocarbon solvent, such as ether or other low-boiling solvent, and the extract recovered by evaporation of the solvent. The preparation of 'l-tetradecylcarboxy-3,4-dicarboxy-2-thiabutane, is given to illustrate the specific example of the method of preparation. Twenty-five hundredths moles of maleic acid is neutralized with a sodium hydroxide solution and an alcoholic solution of tetradecyl thioglycolate (0.25 mole) added to the neutralized acid. The mixture is stirred at room temperature until titration of a small sample of the reaction product with iodine indicates that the addition is substantially completed; this usually requires five to six hours. then acidified with hydrochloric acid, extracted with ether, and the extract recovered by evaporation of the ether.

Although. the esters of 1,3,4-tricarboxy-2-thiabutane of the type described herein can be suitably employed in organic compositions, particularly oleaginous compositions in general, to inhibit or prevent rusting and/or corrosion, for

The mixture is 4 hibits rusting of the type above described. Tho

rust-inhibiting characteristic of turbine oils containing these additives is demonstrated by the following test: Three hundred milliliters of the oil to be tested are placed in a 400 ml. lipless glass beaker and heated to about 140 F. in an oil bath and the oil stirred with a stirrer maintained at about 750 R. P. M. When the temperature of the oil sample reaches about 140 F., a cleaned test strip of cold rolled steel is suspended in the oil and stirring continued for minutes to insure complete wetting of the steel specimen. Thirty milliliters of distilled water are then carefully added by pouring it down the side of the beaker. and stirring continued for forty-eight hours. At the end of this period the specimen is removed from the beaker, washed with naphtha and visually inspected for the presence of rust. The method of carrying out this test is fully described in A. S. T. M. Manual-1942, page 274, and identifled as A. S. T. M.:D665-42T.

Samples of a turbine oil base, namely a hydrocarbon oil having a Saybolt Universal viscosity at 100 F. of about 150 seconds containing small amounts of various esters of 1,3,4-tricarboxy-2- thiabutanes were subjected to the above test and the following results obtained:

TABLE I A. S. T. M. rust test Additive Concentration per cent) Ester l-dodecylcarboxy-3,4-dimrboxy-2-thiabutane: Dis- Moderate. None None. None. None.

tilled Water.

l-tetradecylcarboxy-IiAdicarboxy-2-thiabutane:

Distilled Water Moderate. Slight. None. Do.

Synthetic Sea Water Slight. Do.

to produce more highly refined turbine oils hav-.

ing improved sludging resistant and emulsification properties, the desirable components of oils responsible for the wetting and therefore rustinhibiting qualities of the oil were removed by these refining methods and the stable oils produced became inferior with respect to rust-inhiblting qualities. In steam turbines, rusting is usually encountered in the upper portions of oil reservoirs, and other parts of the system, caused by droplets of water coming in contact with the steel surfaces and displacing the oil with which the surface was covered. An oil will provide adequate protection against this rusting only if it wets the steel surfaces preferentially as compared with water. In the presence of oils which provide no protection coating, the steel surfaces are attacked by water with the formation of ferric oxide and black magnetic oxide. As the rusting progresses these oxides scale off and may be carried in suspension in the oil, often scoring bearings, plugging oil lines and often causing faulty operation or sticking of delicate governor parts. The need for non-rusting turbine oils is therefore great.

In accordance with the present invention the addition of small amounts of the herein-described thiabutanes to turbine oils effectively in- In addition to the A. S. T. M. rust test the inhibited oils were subjected to the so-called Shell tenacity test. This test is carried out as follows:

At the end of the A. S. T. M. D-665-42T test, described above, the steel test specimen are removed from the oil, the oil is replaced with distilled water and the same test specimen then suspended in the beaker. Stirring is then continued at about F. and the test specimen examined periodically for rusting.

The following samples were subjected to the above test and the results obtained tabulated in Table II:

Sample 1.Control (mineral turbine oil base stock of about S. S. U. at 100 F.)

Sample 2.--Control+0.02% l-dodecylcarboxy- 3,4-dicarboxy-2-thiabutane.

Sample 3.Control-|-0.03% l-dodecylcarboxy- 3,4-dicarboxy-2-thiabutane.

Sample 4.Control+0.02% 1 tetradecylcarboxy-3,4-dicarboxy-Z-thiabutane.

Sample 5.Control+0.03% 1 tetradecylcarboxy-3,4-dicarboxy-2-thiabutane.

TABLE II 011 Sample 24 Hours 48 Hours Severe 2 Very Slight...

None None. 4 o. Do. 5 ..do Do.

While the herein-described esters are especially well adapted for use in'turbine'oil compositions,

they can be used in small proportions, namely up to about 2% or more, if required, as anti-rust or anti-corrosion agents for metals, in a wide variety of media, illustrated by the following:

Motor fuels; for example, automobile or aviation gasolines, tractor fuels, Diesel engine fuels, alcohol-containing motor fuels; Lighting and heating fuels; kerosene, stove oils, stove and lighting naphthas, furnace oils, fuel oils;

"Solvent naphthas; cleaner naphthas, such as Stoddard solvent, Y. M. and P; naphthas, hydroformed naphthas;

Lubricating and dielectric oils, motor oils, Diesel oils, aviation engine oils, marine engine lubricants, ear oils, oil field machinery lubricants, icemachine oils, steam cylinder lubricants,;transmission oils, soluble oils, textile oils, cutting oils, turbine oils, insulating oils;

Lubricating greases, stable gel-like or solid dispersions of metal soaps in hydrocarbon oils; Protective coatings, slushing oils and greases in which part or all of the hydrocarbon oil may be replaced by metal soaps and/or waxes such as the ester-type waxes, mineral waxes such as petrolatum and paraflin waxes, pitches, tars,

asphalt rosin.

The compositions, such as for example, the hydrocarbon oil compositions, in which the ester is used, can in addition contain V. I. improvers,

viscosity-increasing agents, bloom producing agents, extreme pressure agents, antioxidants, dyes, and antiknock agents, as the case may be provided only that these additional agents do not enter into appreciable chemical reaction with the ester or precipitate it from the oils to which it has been added.

N Thus, in turbine. oils, we can in addition to an ester, add an antioxidant such as the polyhydric phenols and their alkyl derivatives, for example,

I 3. A normally non-gaseous petroleum oil fraction containing from about 0.001% to about 2% of a 1,3,4-tricarboxy-2-thiabutane having the general formula in which the substituents R, R and R" are selected from the group consisting of hydrogen and an alkyl radical and in which at least one of the Rs is hydrogen and at least one of the R's is an alkyl radical having at least 10 carbon atoms.

4. A hydrocarbon oil containing from about I 0.001% to about 2% of a 1,3,4-tricarbo1w-2- thiabutane having the general formula 0 in which the substituents R, R ,and R" are selected from the group consisting of hydrogen and an alkyl radical and in which at least one of the Rs is hydrogen and at least one of the Rs is an alkyl radical having at least 10 carbon cathechol, tertiary butyl catechol, octyl catechol,

etc. Other eilective antioxidants include betanaphthol, amyl beta-naphthol, octyl beta-' naphthol, lauryl beta-naphthol, alpha-naphthol, amyl alpha-naphthol, N-phenyl alpha-naphthyl-- a'mine, di-alpha-na'phthylamine, and the like.

The antioxidant may suitably'be. used in a proportion in the range of about 0.001% to about 0.5% (by weight) based on the oil.

we claim:

1.. An oleaginous material containing from about 0.001% to about 2% of a 1,3,4-tricarboxy- 2-thiabutane having the general formula in=which the substituents R, R' and R' are selected from the group consisting of hydrogen andan' alkyl radical and in which at least one of the Rsis hydrogen and at least one of the Rs is an alkyl radical having at least 10 carbon atoms. 2. An oil containing from about 000196 to about 2% of a 1,3,4-tricarboxy-2-thiabutane having the general formula ooa (10cm IOOlv' in which the substituents R, R and R" are 'tricarboxy-2-thiabutane.

atoms.

5. A hydrocarbon oil containing from about 10. A hydrocarbon oil containing 0.001% to about 2% of 1-'-cetylcarboxy-3,4-di carboxy-2-thiabutane. I

11. A composition consisting essentially of a hydrocarbon oil and from about 0.001% to about 2% of a 1,3,4-tricarboxy-2-thiabutane having the general formula v H H r n-( -JJ s-o-n (Boon (Boom $00K" in which the substituents R, R and R" are selected from the group consisting of hydrogen and an alkyl radical and in which at least one of the Rs is hydrogen and at least one of the Rs is an alkyl radical having from 10 to 16 carbonatoms.

LEONARD A. MA'I'I'ANO.

LAWSON W. MIXON.

REFERENCES CITED The following references are of record in the file of this patent: 1 i

selected from the group consisting of hydrogen and an allgyl radical and in which at least one o! the R's is hydrogen and at leastone of. the

R's is an alkyl radical having at least 10 carbon UNITED STATES PA'I'En'rs Number Name Date 2,371,143 Barnum Mar. 13, 1045 2,371,207 Zublin Mar. '13, 1945 2,462,200 Kleinholz Feb. 22, 1949 2.474.604 Wasson June 28, 1949 from about Y

Claims

1. AN OLEAGINOUS MATERIAL CONTAINING FROM ABOUT 0.001% TO ABOUT 2% OF A 1,3,4-TRICARBOXY2-THIABUTANE HAVING THE GENERAL FORMULA