US2688595A

US2688595A - Lubricants

Info

Publication number: US2688595A
Application number: US129170A
Authority: US
Inventors: Fainman Morton
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1949-11-23
Filing date: 1949-11-23
Publication date: 1954-09-07
Anticipated expiration: 1971-09-07

Description

, .rosion and/or rusting of metal surfaces.

Patented Sept. 7, 1954 LUBRICANTS Morton Fainman, Chicago, Ill., assignor to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application November 23, 1949,

Serial No. 129,170

7 Claims. i

This invention is directed to improvements in oleaginous compositions and more particularly relates to stable, corrosion and/ or rust inhibiting hydrocarbon oil compositions.

Organic substances such as normally nongaseous hydrocarbon products, particularly petroleum products, such as lubricating oils, turbine oils, insulating oils, greases, waxes and nonviscous petroleum products, such as naphthas, gasolines, fuel oils, as well as synthetic hydrocarbon oils, are susceptible to oxidative deterioration. This oxidation takes place under prolonged storage at atmospheric temperatures, as Well as during use under elevated temperatures. Oxidative deterioration of this type is also encountered with fats and fatty materials, such as animal, vegetable and marine oils, for example, cottonseed oil, corn oil, lard oil, tallow, menhaden oil, etc.

In many types of machinery and industrial equipment in which Water or steam or other aqueous liquids are used which may become contaminated with such aqueous media, rusting and/ or corrosion of the metal. parts is encountered although oil may come in contact with such metal parts. For example, in internal combustion engines, water due to condensation accumulates and causes rusting and/or corrosion of the ferrous metal parts of such engines. In the operation of steam turbines, rusting or corrosion of the ferrous metal parts of such systems is also a serious problem and the prevention or inhibition of such rusting and/or corrosion is highly important. Corrosion is also a serious problem in the operation of textile machinery, in shock absorbers, in hydrauli lifts, etc. Although equipment of the foregoing type usually employ an oil of some sort, the oil film which may form on the metal surfaces does not provide adequate protection against rusting and/or corrosion by the aqueous media due to the partial displacement of this oil film from the metal surfaces.

It is an object of the present invention to provide organic compositions which are resistant to oxidative deterioration and which prevent cor- Another object of the invention is to provide a composition containing an oleaginous material which is resistant to oxidative deterioration and which will prevent the rusting and/or corrosion of metal surfaces with which it comes in contact. A further object of the present invention is to provide compositions containing petroleum products which are resistant to oxidative deterioration and which are also effective in preventing rusting and/or iii v or different alkyl radicals.

corrosion of metal surfaces coated with a film of said petroleum composition. Still another object of the invention is to provide a petroleum oil composition which is resistant to deterioration due to oxidation and which is capable of preventing rusting and/or corrosion of metal surfaces in contact with such petroleum oil compositions. Other objects and advantages will become apparent from the following description thereof.

I have discovered that the foregoing objects can be attained by incorporating in organic compositions of the type hereinafter described, particularly petroleum products, such as petroleum oils, a small amount, sufficient to inhibit oxidative deterioration and to inhibit rusting and/or corrosion, of an oil-soluble ammonium salt of an arylol acid ether obtained by reacting equimolar proportion of an amine and an arylol acid ether at a temperature of from about 50 F. to about 300 F., and preferably from about 150 F. to about 250 F. The amine used is preferably an amino compound known to possess antioxidant properties, particularly the aromatic amino compounds, such as for example, p-amino phenylbeta-naphthylamine, N-phenyl-p-phenylene diamine, p-amino acetinalide, o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, benzidine, p,pdiamino diphenyl methane, etc., and alkylene diamines, such as for example, 1-2 diamino ethane, 1-2 diamino butyl ethane, propylene polyamine, ethylene diamine, etc.

The arylol acid ether is preferably one having the general formula wherein R and R are substituents selected from the group consisting of hydrogen or an alkyl group, A is a substituent selected from the group consisting of hydrogen or the group wherein R and R are as above, R" is a substituent selected from the group consisting of hydrogen, aryl, alkyl, aralkyl, alkaryl, and mixtures thereof, and n i an integer of from 1 to 4, inclusive, and wherein R plus R contains 10 to 30 carbon atoms. R, R and B may be the same In the above formula 3 the ring structure represents a monoor polynuclear aryl nucleus, such as phenyl, naphthyl,

etc. groups.

The preferred compounds are those in which A is hydrogen and n is 1 or 2.

Representative of specific examples of compounds coming within the above general formula are the following:

Catechol mono-alpha-stearic acid ether 4 100 F. of about 100 seconds to 350 seconds are employed. With the advent of drastic refining treatments to produce more highly refined turbine oils having improved color, etc., desirable components for preventing the oxidative deterioration of the oils and these responsible for the wetting and therefore rust inhibiting qualities of the oil are removed. To overcome the susceptibility of such oils to oxidative deterioration and to impart rust inhibiting properties thereto, small 2222: 351 i 'gggfi i i fig ggi 32 ther amounts, of the order above stated, of the reac- Hydroquinone m l a1pha stgari c i ether tion product of an amine and an arylol acid ether I-Iydroquinone di-alpha-stearic acid ether fi g g'fi g? igg g 2 13:: Naphthalene-1,5-di-alpha-stearic acid ether 1 .g e i 0Y1 n hich Phloroglucinol mono-alpha-stearic acid ether W 2, ,1 o a W Phloroglucinol di-alpha-stearic acid ether i 1. i m {b1 fi mgfior 5 3 Phloroglucinol tri-alpha-stearic acid ether 011 g fi g f g Catechol mono-alpha-lauric acid ether g o gmversa vlscos a 0 1 Resorcinol lauric stearic acid ether of 6 sewn. S gl 8 Hydroqu-mone dimalmitic acid ether of various ammonium sa ts of e presen inven- Catechol monmamhwoleic acid ether 1310B. and subjected the followmg oxidat on Resorcinol monmmontanic acid ether test. The oil composition 1s heated and mainphl l i monmbahenic acid ether tamed at a temperature of about 100 F. while C t monmlinoleic acid ether 2r blowing oxygen therethrough, and at stated pe- Pyrogallol mono-stearic acid the 0 riods a sample of the oil is withdrawn to determine the neutralization number thereof and the The ammonium salts of arylol acid ethers are test continued for 336 hours or until a sample eemphfied by the j g compounds has a neutralization number of 2. The neu- Dl-bu yl-p-ph n l n xy tralization number is determined by adding two oxy-alpha-stearate grams of the sample to a neutral solution of 200 Para-ammo PhenylB'naphthylammomum'9'1- cubic centimeters of naphtha and 100 cubic cenpha-alpha-dihydroxy-p fy stealate timeters of 95% ethyl alcohol containing phenol- Phenyl-alpha-naphthylammomum-alphapara phthalein. The mixture is then titrated with dlhydrexyphenoxy Steamte N/10 sodium hydroxide to the first pink color. l'z'dlammo ethane ortho dlhydmxyphenoxy The neutralization number is calculated from the at??? d t h d h b equation:

y e e iamme symr1 y roxyp eno ehenate Xy c. c. NaOH norma1ity 56.1

Neutralization No. Para-ammo-acetamhde alpha ortho dihy- 40 Welght of Sample droxy-phenoxylaurate Butylethanolammonium-2-hydroxy-phenoxyal- The data obtained in the foregoing test are pha-stearate, etc. tabulated in Table I.

TABLE I Oxidation test Time Until Neu- Appearance of Sample No. tralization No. of Sample After Sample Equals 2 Test Hours 1-Control (no additive) 8 Red-brown sludge. 2Control+.l% 2-hydroxy phenoxy- 20 No sludge.

alpha-stearic acid. 3Contr0l+.1% di-butyl-p-phenylene 160 D0.

di-amlne-2-hydroxy-phenoxy-alphastearate. 4Control+.l% P-amino phenyl-fi- 336 Do.

naphthylammonium-2-hydroxy phenoxy-alpna-stearate. 5Contro1+.l% Phenyl-alpha-naph- 320 Do.

thyl ammonium 2 hydroxy phen oxy-alpha-stearate.

It is not intended to imply that all amine salts of arylol acid ethers serve with identical efficiency; while they are all effective, they will exhibit some variation depending upon the nature and severity of the service to which they are subjected. In general, it will be found. that from about 0.0005% to about 2.0%, and preferably from about 0.003% to about 0.5% by weight of the ammonium salt of arylol acid ether will provide adequate protection.

For the purpose of illustrating the present invention the same will be described as applied to steam turbine lubrication for which highly re- The effectiveness of these additives in inhibiting rusting is demonstrated by the results obtained in the A. S. T. M. test for rust prevention, having the designation D665-47T. In this test 300 cc. of the oil to be tested are placed in a 400 cc. lipless glass beaker and heated to 140 F. in an oil bath and the oil sample agitated with a stirrer maintained at about 1000 R. P. M. When the temperature of the oil sample reaches 140 F., a cleaned test strip of cold rolled steel is suspended in the oil and the stirring continued for thirty minutes to insure complete wetting of the steel specimen. Thirty cc. of distilled water are then carefully added to the beaker and the stirfined oils having Saybolt Universal viscosities at ring continued for 48 hours. At the end of this time the steel specimen is removed from the beaker, washed with naphtha and visually inspected for the presence of rust. 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 salts of the type herein described were subjected to this test and the results obtained tabulated in Table II.

The above data demonstrate the effectiveness of very small amounts of the additives in the present invention in inhibiting rusting.

Compositions containing the herein described ammonium salts of arylol acid ether can also contain in addition pourpoint depressors, extreme pressure agents, viscosity improvers, detergents, etc.

While I have described my invention by reference to a specific embodiment thereof, the invention is not limited thereto, but includes within its scope such modifications and variations as come within the spirit of the appended claims.

I claim:

1. A composition comprising essentially a major proportion of an oil and an oil-soluble aromatic amino salt obtained by reacting an arylol carboxylic acid ether with an aromatic amino compound selected from the class consisting of a naphthylamine, a phenylenediamine and pp diamino diphenyl methane, said salt being used in small but sufiicient amounts to inhibit the oxidative deterioration of said oil and to impart a corrosion-inhibiting property to said oil.

2. A composition as described in claim 1 in which the arylol carboxylic acid ether has the general formula 0 OH u 6 wherein R and R are substituents selected from the group consisting of hydrogen and an alkyl group, A is a substituent selected from the group consisting of hydrogen and the group R 8-H JOOH in which R and R. are as above described, R is a substituent selected from the group consisting of hydrogen, aryl, alkyl, aralkyl, alkaryl radicals, and mixtures thereof, 11. is an integer of from 1 to 4, inclusive and wherein R plus R contain from about 10 to about 30 carbon atoms.

3. A composition comprising essentially a normally non-gaseous petroleum fraction and from about 0.0005% to about 2.0% of an oil-soluble aromatic amino salt obtained by reacting an arylol carboxylic acid ether with an aromatic amino compound selected from the class consisting of a naphthylamine, a phenylenediamine and a pp diamino diphenyl methane.

4. A composition as described in claim 3 in which the arylol carboxylic acid ether is an arylol stearic acid ether.

5. A composition comprising essentially a hydrocarbon oil and from about 0.0005% to about 2.0% of di-butyl-para-phenylenediamine-2-hydroxy-phenoxy-alpha-stearate.

6. A composition comprising essentially a hydrocarbon oil and from about 0.0005% to about 2.0% of para-amino phenyl-beta-naphthylammonium-2-hydroxy-phenoxy-alpha-stearate.

7. A composition comprising essentially a hydrocarbon oil and from about 0.0005% to about 2.0% of phenyl-alpha-naphthylammonium-2- hydroxy-phenoxy-alpha-stearate.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,198,293 Reiff et al. Apr. 23, 1940 2,252,665 'Reiff et a1. Aug. 12, 1941 2,426,496 Farley Aug. 26, 1947 2,447,483 Baker Aug. 24,- 1948 2,459,717 Perry Jan. 18, 1949 2,470,276 Watkins May 17, 1949 OTHER REFERENCES Lubricating Oil Additives, by Kalichevsky, in Petroleum Refiner, vol. 28, No. 10, pages 127 and 128.

Polar Type Rust Inhibitors, I. and E. Chem., vol. 40, No. 12, pages 2338 to 2347, page 2343 pertinent.

Claims

1. A COMPOSITION COMPRISING ESSENTIALLY A MAJOR PROPORTION OF AN OIL AND AN OIL-SOLUBLE AROMATIC AMINO SALT OBTAINED BY REACTING AN ARYLOL CARBOXYLIC ACID ETHER WITH AN AROMATIC AMINO COMPOUND SELECTED FROM THE CLASS CONSISTING OF A NAPHHYLAMINE, A PHENYLENEDIAMINE AND PP'' DIAMINO DIPHENYL METHANE, SAID SALT BEING USED IN SMALL BUT SUFFICIENT AMOUNTS TO INHIBIT THE OXIDATIVE DETERIORATION OF SAID OIL AND TO IMPART A CORROSION-INHIBITING PROPERTY TO SAID OIL.