US2938870A

US2938870A - Extreme pressure lubricating oil containing sulfur-chlorinated esters of chlorendic acid

Info

Publication number: US2938870A
Application number: US602061A
Authority: US
Inventors: Dorinson Amos
Original assignee: Sinclair Refining Co
Current assignee: Sinclair Refining Co
Priority date: 1956-08-03
Filing date: 1956-08-03
Publication date: 1960-05-31
Anticipated expiration: 1977-05-31

Description

United States Patent EXTREME PRESSURE LUBRICATING OIL (ZON- TAINING' SULFUR-CHLORINATED ESTERS OF CHLORENDIC AClD Amos' Dorinson, Homewood, 111., assignor to Sinclair li eglning Company, New York, N'.Y., a corporation '0 ame N0 Drawing. Filed: Aug. 3, 1956, Ser. No. 602 061 5 Claims. (Cl. 2 52-4'8.4)

This invention relates to. sulfur-chlorinated esters of chlorendic acid, and particularly to the use of such esters in mineral oils to provide extreme pressure lubricants and metaleworking oils having improved properties. This invention further relates to extreme pressure lubricants of improved load carrying ability which satisfy the requirements demanded in the lubrication of bearing, gears, and the like, subjected to heavy loads per unit area of surface.

The present invention is particularly concerned with cutting oils used in broaching, gear cutting, hobbing, planing and similar operations in which metal is removed from the work piece at a comparatively low rate, e.g. at cutting speeds of to 20 surface feet per minute. The metal chips removed vary in. thickness from 0.005 to 0.0005 inch. A major objective of cutting operations of this type is the achievement of a good surface finish, and, therefore, one of the functions of a cutting oil used in such operations is to improve the surface finish obtained.

Certain short-chain chlorinated compounds such as carbon tetrachloride, ethylene dichloride and diisobutylene dichloride are known to be especially effective as additives for broaching and gear cutting oils. Although an excellent surface finish can be obtained on work pieces by the inclusion of carbon tetrachloride in broaching and gear cutting oils, this compound is not suitable as" a-cut-- ting oil additive for two reasons. First, due to its volatility carbon tetrachloride is rapidly lost by evaporation from the cutting oil during use thus necessitating close control of the concentration and frequent replenishment with fresh carbon tetrachloride. Second, carbon tetrachloride is a toxic substance which causessevere physiological damage when inhaled as a vapor or when absorbed through the skin by contact. Ethylene dichloride is also highly volatile. Diisobut'ylene dichloride, which might be used as a. substitute for carbon tetrachloride due to its lack of toxicity, is'objectionable because of its highly on pleasant odor which could not be tolerated for the'length of an average working day. Therefore, a need exists for a non-toxic, non-volatile, substantiallyodorless, mineral oil-soluble additive which imparts extremepressure properies to a cutting oil composition.

In accordance with the present invention Ihave discovered that valuable extreme pressure'additives can be prepared by sulfur-chlorinating unsaturated esters of chlorendic acid and that the addition of such additives to mineral lubricating oils provides extreme pressure lubricating compositions of improved load' carrying ability under conditions of high mechanical loading. As cutting oils or metal working fluids, mineral oils which contain sulfur-chlorinated esters of chlorendic acid, are useful in reducing the surface roughness of machined parts.

The oil-soluble sulfur-chlorinatedesters added to mineral lubricating oils in preparing; lubricating compositions of this invention canv be obtained by sulfur-chlorinating, anoil-soluble ester of chlorendic acid of thefollowing formula:

in which R is an unsaturated aliphatic, including cycloaliphatic, hydrocarbon group containing 3 to. 20 carbon atoms and R is hydrogen or the identical or non-identical member selected from the same group as R. More specifically, the unsaturated members'includ'e alkenyl groups such as allyl, oleyl, cyclohexenyl and ester groups from unsaturated alcohols derivedfrom acids such as linoleic', myristoleic, cinnamic, angelic and'the like; which unsaturated members can, if desired, be substituted as withchlorine for instance. Although the monoesters can be employed, the preferred esters of chlorendic acid are di'-' esters and particularly those in which the ester groups are mono-olefinic and contain from 16 to 18 carbon atoms. A preferred diester can be obtained from the un-- saturated alcohols derived from sperm oil The esters can be prepared by any suitable method as, for example, by reacting chlorendic anhydride with an excess of the appropriate unsaturated alcohol. The esterification reaction can be carried out in the presence of a catalyst such as p-toluene sulfonic acid until the theoretical amount of water has been removed. Alternatively, chlorendic acid maybe used instead of the anhydride and inane method two moies'of water are evolved for each mole of chlorendic diester formed. The water of reaction may be removed azeotropically by distillation with a solvent such as benzene or toluene.

The sulfur-chlorination of the chlorendic acid ester is accomplished by reacting each mole of chlorendat'e ester with about .5 to 2 moles of a sulfur chloride such as sulfur monochloride or sulfur dichloride at a temperature in the range of about to 300 F. Frequently, the exothermic heat of reaction will maintain the reaction mixture within the desired temperature range although in large scale preparations it may be necessary to use ex-- ternal cooling means.

In oil blends which are usedas metal working fluids in operations such as planing, .broaching, gear cutting and the like, the amount of additive employed can depend upon the particular ester in the additive. For esters of high molecular Weight, for example, sulfur-chlorinated oleyl chlorendate diester, the amount employed will usually be about 9 to 35% by weight whereas for the lower molecular Weight esters, such as sulfur-chlorinated diallyl chlorendate, the amount used in general will range from 5 to 30% by weight. The compounding of oils for extreme pressure lubricants frequently requires about 0.5 to 10% of the sulfur-chlorinated chlorendate ester. These percentages are based on the weight of the mineral oil present. The manner in which the sulfur-chlorinated es-- esters of chlorendic acid are prepared and'the proper ties of lubricating oils containing the esters are illustrated in the following examples which are not to be considered as limiting.

EXAMPLE I Preparation of oleyl ch l orendate di ester A mixture of 705 grams of chlorendic anhydride and 1000 grams of commercial oleyl alcohol (hydroxyl number 214, iodine number 83) was dissolved in 1000 cc. of xylene and 10 grams of p-toluene sulfonic acid were added added as a catalyst. The mixture was heated to reflux for 10 hours until 44 cc. of water had been col.- lected in a Dean-Start trap attached to the esterificationapparatus. The reaction mixture was then washed once with 0.25 N KOH in 1:1 alcohol-water and twice with 1:1 alcohol-water. After clarification by filtration, the reaction mixture was freed of xylene by distillation and the last traces of solventwere removed under vacuum at a pot temperature of 300 F. The reaction product was a dark oily liquid with the characteristics listed below.

Percent chlorine; 24.0 Acid number 0.28 Saponification number 127.9 'Iodine number 50.1

EXAMPLE II Preparation of allyl chlorendate diester A mixture-of 1500 grams chlorendic anhydridedissolved in 2000 cc. of allyl alcohol with 10 grams of ptoluene sulfonic acid as a catalyst was refluxed for 32 hours and the excess allyl alcohol was removed by dis;

tillation. The residue was taken up in a mixture of pen-. o

tame and benzene and was washed first with -aqueous KOH and then with water.- The solvent was distilled off, first at atmospheric pressure and finally at 2-3 mm. pres sure. The product was a dark viscous liquid having the following characteristics.

Percent chlorin I 44.8

Acid number; 0.10

Saponification number 236.8

Iodine number 107.1

EXAMPLE III Sulfur-chlorination of oleyl chlorendate diester A portion of oleyl chlorendate diester containing 22.6% chlorine, with a saponification number of 119.4 and arr-iodine number of 50.0, was reactedwith sulfur monochloride. To 1541grams of the di-oleyl chlorendate, 208 grams of sulfur monochloride were added at 140167 F. and the reaction mixture was stirred for 6 hours at 158 F.. The reaction mixture was then blown with air at 140 F. to purge it of free hydrogen chloride, and the further evolution of hydrogen chloride was inhibited'by the addition of 0.2% of propylene oxide. The product a thick, sticky, dark brown substance at room temperature,- contained 5.85% sulfur and 25.8% chlorine. 1

EXAMPLE IV Szilfur-chlofination of allyl chlorendate diester To 600 grams of allyl chlorendate diester, 115 grams ii ofsulfur monochloride were gradually added at a temperature of 195210 F. The reaction mixture thickened progressively and eventually became so viscous that further stirring was impossible. This tacky, semi-solid material contained 7.18% sulfur and 44.7% chlorine.

EXAMPLE V w Compounded oils containing sulfur-chlorinated oleyl chlorendate diesters Compounded oils were prepared with sulfur-chlorinated (Ii-oleyl chlorendate, as prepared in Example HI, by blending the additive into acid refined Coastal naphthenic oils at 150 F. to 210 F. The additive remained .completely dissolved in the oil at room temperature.

The following blends were made up in mineral oils of different viscosities.

' Percent Percent Viscosit Blend N o. Additive PercentS O SUS at g 7 100 F.

4 EXAMPLE v1 Compounded oils containing sulfur-chlorinated allyl chlorendate diester Eighty parts of the sulfur-chlorinated diallyl chlorendate of Example IV were mixed with parts of benzene to aid in blending the additive into oil. Seven hundred and. eight-seven grams of this mixture were added to i 5025 grams of an acid-refined Coastal oil of'17S seconds viscosity at 100 F. It was found necessary to add 1839 grams of benzene to keep the sulfur-chlorinated diallyl chlorendate completely dissolved in the oil at room temperature. The final blend, which had'8.25% of sulfurchlorinated diallyl chlorendate incorporated therein, contained 0.79% sulfur and 3.28% chlorine; and had a viscosity of 96.6 SUS at F.

EXAMPLE VII Sulfur-chlorinated chlorendate esters as metal-working additives The advantages obtained by employing the lubricating compositions of the present invention as cutting oils become particularly apparent in cases where the surface finish requirements for thework piece are unusually,

stringent. The effect of oil blends containing sulfurchlorinated oleyl chlorendate diester as a cutting oil was demonstrated by means of an orthogonally cutting planer operation. As shown below, the various oil blends prepared in accordance with Examples V and VI were rated.

according to the surface roughness of the cut surface as determined by a profilometric measuring instrument. Results arev shown in Table I below- 1 Blends prepared in Example V.

Oil blends containing sulfur-chlorinatedoleyl chlorendate diester were tested for extreme-pressure load carry-. ing ability in the Falex lubricant testing apparatus, Also an oil blend containing 26% by weight of a non-sulfurchlorinated oleyl chlorendate'diester was tested. In this test an uncompounded mineral oil does not allow the test to run for the three-minute breakin period at 300 lbs. load without failure. As can, be seen, the sulfurchlorinated diesters provide extreme pressure lubricants.

of improved load carrying ability.

TABLE II Oil Blend Percent Failure Additive Load, Lbs.

2 10 8 4, 500V 4 1 5 3 4, 500 5 l 2 1, 500 7 2s 1, 250

1 Blends prepared as in Example V.

1 26% Oleyl chlorendate in oil.

I Did not fail at load limit of the apparatus.

I claim: I I p p 1. A new composition of matter consisting essentially of a mineral lubricating oil and an amount suflicient to increase the, load carrying capacity of the oil'of a sulfurchlorinated oil-soluble ester of 'chlorendic acid produced by reacting a sulfur chloride and an oil-soluble chlorendic acid ester in a ratio of'about .5 to 2 moles of sulfur chloride to 1 mole of said chlorendic' acid ester wherein 1 Blend of Example VI.

5 6 said ester group is an unsaturated aliphatic hydrocarbon References Cited in the file of this patent radical containingi rom 3 to 2 0 carhon atoms. UNITED STATES PATENTS 2. The composition of claim 1 in which the ester is about 5 to 35% of the mineral oil. 2,156,265 M11181 May 2, 1939 3. The composition of claim 1 in which the ester is 5 2,157,873 Peskl May 1939 about (L5 to of the mineral oil et 2 4. The composition of claim 2 in which the ester is a 2,387,286 f 1945 diester in which each ester group contains from 16 to 18 2,433,853 LmcPln et a1 1948 carbon atoms NOV. 30, 2,771,423 Dorinson Nov. 20, 1956 5. The composition of claim 4 in which the ester is a 10 diester in which eachester group contains from 16 to 18 carbon atoms.

Claims

1. A NEW COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL AND AN AMOUNT SUFFICIENT TO INCREASE THE LOAD CARRYING CAPACITY OF THE OIL OF A SULFURCHLORINATED OIL-SOLUBLE ESTER OF CHLORENDIC ACID PRODUCED BY REACTING A SULFUR CHLORIDE AND AN OIL-SOLUBLE CHLORENDIC ACID ESTER IN A RATIO OF ABOUT .5 TO 2 MOLES OF SULFUR CHLORIDE TO 1 MOLE OF SAID CHLORENDIC ACID ESTER WHEREIN SAID ESTER GROUP IS AN UNSATURATED ALIPHATIC HYDROCARBON RADICAL CONTAINING FROM 3 TO 20 CARBON ATOMS.