US2643979A

US2643979A - Demulsifiable lubricant compositions

Info

Publication number: US2643979A
Application number: US196947A
Authority: US
Inventors: Albert W Lindert
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1950-11-21
Filing date: 1950-11-21
Publication date: 1953-06-30
Anticipated expiration: 1970-06-30

Description

Patented June 30, 1953 DEMULSIFIABLE LUBRICANT COMPOSITIONS Albert W. Lindert, Homewood, 111., assignor to Standard Oil Company, Chicago, 111., a. corporation oflndiana N Drawing. Application November 21,- 1950, Serial No. 196,947

13 Claims. (Cl. 252-461) This invention relates to improvements in lubricant compositions, and more particularly relates to compositions having improved demulsibility characteristics and to the method of preparing the same.

a In many applications of lubricant compositions, such as gear lubricants, extreme pressure lubricants, etc., which contain one or more additives, such. as soaps, organic halogenated compounds, sulfur-containing compounds, etc., to impart desired properties to such lubricants, the products become contaminated with water with the formation of relatively stable oilin-water emulsions. If the lubricant composition does notreadily demulsify or separate from the Water, the use of such products as lubricants is materially decreased and must often be discarded.

It is an object of the present invention to provide a lubricant composition having improved demulsibility characteristics. Another object of the invention is to provide a compounded lubricant composition which will readily separate from Water when contaminated with or emulsified with water. A still further object of the invention is to provide a lubricant composition which is resistant to the formation of oil-in-water emulsion, when used in the presence of water or when contaminated with water. Another object of the invention is to provide a method of improving the demulsibility characteristics of lubricant compositions. Other objects and advantages of the present invention will become apparent from the following description thereof.

In accordance with the present invention lubricant compositions having improved demulsibility characteristics are obtained by incorporating in such lubricants 0.002% to about 5%, and preferably from about 0.02% to about 1% of a quaternary ammonium compound having the general formula:

R Rat-R HaJ Hal D EN/ in which the Rs represent the same or different alkyl, aralkyl, aryl groups or combinations thereof, Hal represents a halogen atom, such as chlorine,bromide, iodine, etc., DEN'i-e'presents a het: erocyclic compound, such as pyridine, and R. 1s an alkyl group of at least about 8' carbon atoms.

In the above formula at least one R is an alkyl group having 1 to 3 carbon atoms, and at least one B. is an alkyl group having at least8car'bonatoms, and preferably 10 to 20 carbon atoms. Compounds formed by substituting one or more of the hydrocarbon substituents groups with a halogen, oxygen or sulfur are also suitable. Illustrative of specific compounds defined by the above formulas are the following:

Triethyl-dodecylthiomethyl ammonium chloride Benzyl-d-imethyl-dodecyloxymethyl ammonium chloride Methyldodecylbenzyltrimethyl ammonium chloride Hexadecyl pyridinium bromide Dimethyl-dilauryl ammonium bromide Dimethyl-didecylthioethyl ammonium chloride Methyl-diethyl-dodecylth'ioethyl ammonium iodide Trimethyl decylmethylaminoethyl bromide Hexadecylthiomethyl pyridinium chloride ammonium The lubricant composition in whichthe quaternary ammonium compounds of the type herein described find utility are those compositions which containin addition to the viscous hydrocarbon lubricating oil, additives which tend to promote the formation of emulsions in the presence of water. Such additives are, for example, soaps of high molecular weight carboxylic acids, such :as vegetable, animal and marine fats and fatty acids, halogen-containing and/or sulfur containing and/or phosphorus-containing organic compounds, such as chlorinated hydrocarbons, sulfurized hydrocarbon oils, esters of acids of phosphorus, organic sulfides, sulfonates, naphthenates, etc. Such additives are usually employed in amounts of from about 0.25% to 15%, or more.

Illustrative of an application of the present invention is the lubrication of gears of heavy machinery in which, because of the high temperatures and pressures encountered, so-called extreme pressure gear lubricants are employed.

Chemical Company. An example is the equip-.

ment used in the rolling of metals. Frequently in the rolling of metals, Water or Water emulsions, known as rolling solutions are sprayed on the rolled sheet to loosen and wash away scale, act as coolant for the rolls and, in the case of rolling solutions to act as rust preventivesp The water on rolling solution frequently contaminates the extreme pressure gear lubricant and emulsions are formed. Heretofore, such emulsions had to be-stored in a quiescent state for sixteen to twenty-four hours or more to permit the stratification and separation of lubricant and water. In accordance with the present invention, the addition of small-amounts of a quaternary ammonium compound of the type hereindescribed enables such emulsions to break and separate in a relatively short time, usually not more than one hour and in many cases in less than ten minutes; the time required for such emulsions to break: and separate depending, of course, on the type ofservice and degree of oil and water'mixing. I

The viscous hydrocarbon oil can, be any hydrocarbon oil, e. g. petroleum'oil, having a Saybolt Universal viscosity within the range of. from about 80 seconds at 100 F. to about 500 seconds at 210 F. The oil can be a distillate or residuum oil or mixtures thereof. The oil may or may not be a solvent-extracted oil. There can also be blended with the hydrocarbon oil asphaltic materials such as heavy residuums or blown or oxidized residuums. The choice of the oil used will be largely determined by the nature of the service for which the lubricant is designed.

The followingexamples are illustrative of types of lubricant compositions for which the present invention is adapted. These examples aregiven solely by way of illustration and are not in- 4 Example IV Per cent Sulfurized sperm oil 22 Chlorinated paraffin Wax containing 40% chlorine 2.75 Lead naphthenate 4.10 Dilauryldimethyl ammonium bromide 0.10 Petroleum oil (S. U. S. at 210 F.-95) 71.05

Example V Per cent Dibenzyldisulfide 2.50 Chlorinated paraffin wax 7.5 Dimethyldodecylbenzyl ammonium chloride 0.075

Petroleum oil 89.925

tended to be indicative of the scope of the invention.

. Example I l Per cent Organic E. P. agent 0.5 --15 Asphalt 0.0 -10 Hydrocarbon lubricating oil '75 --99.5 Quaternary ammonium compound 0.002- 5.0

'Ezmmple II s Per cent Chlorinated hydrocarbon 7.0 Oxidized MC asphalt .4.6 Petroleum oil 89.3 Dilauryldimethyl ammonium bromid 0.1

. 1 Of the type hereinabove described. v

Preferably an oxidized asphalt from res duum, having melting points within the range of about 60- -F. to 100 F., which have been oxidized by air blowing or other suitable means to increase the melting points by an increment of from about 80 F. to about 200 F. r

Dilauryldimethyl ammonium bromide 0.1

. The effectiveness of the quaternary ammonium compounds of the type herein described in improving the demulsibility characteristics of lubricant compositions is demonstrated by the data in the following table. obtained in the following manner: An extreme pressure gear lubricant consisting essentially of: r

Per cent- E. P. agent 1 8.75 MC oxidized asp-halt 5.0

(ASTM penetration at 77 F. 30-40; softening point ring and ball method 175- 185 F.)

after being emulsified with water in the manner described below, showed substantially no water separation after standing sixteen hours at 130 F. In order to demonstrate the eifectiveness of the quaternary compounds in breaking and/or preventing such emulsions, small amounts of such materials were added to the above base formulations and demulsibility determined by the following test:

Fifty-three cubic centimeters of distilled water and twenty-seven cubic centimeters of 'the lubricant were placed in a clean cc. graduate. The graduate and contents were placed in a F. water bath and permitted to remain therein for fifteen minutes. After this period the graduate was placed in a Herschel apparatus (Days Handbook of Petroleum Industry, vol. 1, page 701) and stirred at the standard speed, about 1500 R. P. M. for five minutes. was then stopped, the paddle lifted and cleaned into the graduate. The graduate and contents were placed in the 130 F. water bath and ob.

served, as to the volume of water separated by the end of five minutes and at the end of a .one hour period. A series of tests were made on the above base lubricant and the base lubricant containing 0.1% each of the following quaternary ammonium compounds:

ride Sample ride These data a were The stirrer 5--Dimethylditridecyl ammonium chlo :pyridinium ammoslant 10+Benzyldimethyldodyloxymethyl ammonium chloride" cc. Water-Se ara- 1' av tion;.at;130 Concentra- After After 1 min. hour Percent V 1 None None None 0.0075 20 21 2 0.0375 16 52 0.075 3 52 0.150 6 51 0.0075 19 19 3 0.0375 25 41 0.075 23 27 0.150 25 0.003 19 19 4 0.015 21 22 0.030 27 30 0.060 44 51 0.0036 20 20 6 0.0180 I 10 20 0.036 14 48 0.72 11 51 0.004 11 11 0.020 19 20 6 0.040 24 25 0.080 22 24 0.003 20 20 0. 015 20 22 7 0. 030 21 23 0.060 21 23 0.0037 22 22 8 0.0185 22 22 0. 037 20 34 0.074 28 45 0.0023 19 19 9 0.0115 20 21 0.023 21 22 0.046 43 47 0.0035 17 16 0 0.0175 20 20 1 0.035 22 28 0.07 16 35 As demonstrated by the above data, the addition of small amounts of quaternary ammonium compounds of the type herein described effectively promote the demulsification of oil-in-water emulsions.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

While the present invention has been described by reference to preferred embodiments thereof, the same have been given by way of illustration only and are not limitations of the invention, which includes within its scope such modifications and variations as come within the scope of the appended claims.

I claim- 1. A lubricant composition comprising essentially a major proportion of a hydrocarbon oil of from about 0.5% to about of an organic extreme pressure agent containing an element selected from the group consisting of chlorine, sulfur, phosphorus, and mixtures thereof and normally susceptible to the formation of oil-inwater emulsions in the presence of water, from 0% to about 10% of an asphalt, and from about 0.005% to about 1% of a compound selected from the group consisting of a quaternary compound having the general formula:

in which the .Rs represent radicals selected from the group consisting of alkyl, aralkyl, aryl radicals and mixtures thereof, of which at least one R is an alkyl group of 1 to 3 carbon atoms, and

at least one B. is an alkyl group having at least 8 carbon atoms, and Hal is an halogen atom, and a quaternary compound having the general formula:

in which DEN is aheterocyclic compound, R" is an alkyl group of at least 8 carbon atoms, and Hal is an halogen atom.

2. A lubricant composition as described in claim 1 in which the quaternary ammonium compound is dilauryldimethyl ammonium bromide.

3. A lubricant composition as described in claim 1 in which the quaternary ammonium compound is dimethyldodecylbenzyl ammonium chloride.

4. A lubricant composition as described in claim 1 in which the quaternary ammonium compound is dodecylthiomethyl pyridinium chloride.

5. A lubricant composition as described in claim 1 in which the quaternary ammonium compound is triethyldodecylthiomethyl ammonium chloride.

6. A lubricant composition as described in claim 1 in which the organic extreme pressure agent is a phosphorus-sulfur-chlorine-containing hydrocarbon.

7. A lubricant composition comprising essentially a major proportion of petroleum oil, about 8.75% of a phosphorus-chlorine and sulfur-containing organic extreme pressure agent normally susceptible to the formation of oil-in-water emulsions in the presence of water, about 5% of an oxidized asphalt, and from about 0.02% to about 1% of dilauryldimethyl ammonium bromide.

8. The method of imparting demulsibility characteristics to a lubricant composition normally susceptible to the formation of oil-in-water emulsions in the presence of water, which composition comprises essentially a major proportion of a hydrocarbon oil, from about 0.5% to about 15% of an organic extreme pressure agent containing an element selected from the group consisting of chlorine, sulfur, phosphorus and mixtures thereof, and from about 5% to 10% of an asphalt, which comprises incorporating in said lubricant composition from about 0.002% to about 5% of a compound selected from the group consisting of a quaternary compound having the general formula:

Hal

in which the Rs represent the radicals selected from the group consisting of alkyl, aralkyl, aryl radicals and mixtures thereof, of which at least one R is an alkyl group of 1 to 3 carbon atoms. and at least one R is an alkyl group having at least 8 carbon atoms, and Hal is an halogen 0 atom, and a quaternary compound having the general formula:

/Hal 5 N .in Which DEN is a heterocyclic compound, R. is

a'nalkyl group of at least 8 carbon atoms, and Hal is an halogen atom. r a

. 9. The method of claim 8 inwhich the quaternary ammonium compound is dilauryldimethyl ammonium bromide.

10. The method of claim 8 in which the quaternary ammonium compound is dimethyidodecylbenzyl ammonium chloride. 7

11. The method of claim 8 in which the quaternary ammonium compound is dodecylthiomethyl pyridinium chloride.

12. The method of claim 8 in which the quater- 5 and chlorine-containing hydrocarbon.

. ALBERTW. LINDERT.

References Cited in the file of this patent T D st aw P T Number Name- 7 Date 2,228,325 01in et a1. Jan. 14, 1941 De Groote Aug. 11, 1943

Claims

1. A LUBRICANT COMPOSITION COMPRISING ESSENTIALLY A MAJOR PROPORTION OF A HYDROCARBON OIL OF FROM ABOUT 0.5% TO ABOUT 15% OF AN ORGANIC EXTREME PRESSURE AGENT CONTAINING AN ELEMENT SELECTED FROM THE GROUP CONSISTING OF CHLORINE, SULFUR, PHOSPHORUS, AND MIXTURES THEREOF AND NORMALLY SUSCEPTIBLE TO THE FORMATION OF OIL-INWATER EMULSIONS IN THE PRESENCE OF WATER, FROM 0% TO ABOUT 10% OF AN ASPHALT, AND FROM ABOUT 0.005% TO ABOUT 1% OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A QUATERNARY COMPOUND HAVING THE GENERAL FORMULA: