US3528917A - Sulfurized calcium alkylphenolate lubricant compositions - Google Patents

Description

United States Patent O 3,528,917 SULFURIZED CALCIUM ALKYLPHENOLATE LUBRICANT COMPOSITIONS James G. Dadura and Doris Kivelevich, Fishkill, N.Y.,

assignors to Texaco Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed May 22, 1967, Ser. No. 640,362 Int. Cl. Cm 1/42 US. Cl. 25242.7 9 Claims ABSTRACT OF THE DISCLOSURE The disclosure relates to a lubricating oil composition and method of preparation containing sulfurized normal calcium alkylphenolate detergent-dispersant having superior resistance to oxidative decomposition. The sulfurized normal calcium alkylphenolate additive ingredient is prepared by the sequential or simultaneous reaction of alkylphenol with a calcium alkoxyalkoxide and sulfur in the presence of a hydrocarbon lubricating oil, said reaction most desirably followed by a deodorizing treatment of the resultant product utilizing carbon dioxide.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is related to co-assigned ,Ser. No. 624,193, filed Mar. 20, 1967.

BACKGROUND OF INVENTION Field of invention This invention is in the field of art relating to fluent compositions specialized and designed for use between two relatively moving surfaces in contact therewith for reducing friction therebetween and preserving the surface. The lubricant compositions of the invention contain a compound which has a calcium component linked to a carbon through an oxygen.

Prior art It is well known that lubricating oils tend to deteriorate under the conditions of use in present day diesel and automotive engines with attendant formations of sludge, lacquer and resinous materials which adhere to the engine parts particularly the piston ring, groove and skirt, thereby lowering the operating efficiency of the engine. To counteract the formation of these deposits certain chemical additives have been found which when added to lubricating oils have the ability to keep the deposit forming materials suspended in oil so that the engine is kept clean and in eflicient operating conditions for extended periods of time. These agents are known in the art as detergents or dispersants. Metal organic compounds are particularly useful in this respect. One class of metal organic compounds which have been found so useful are the sulfurized normal calcium alkylphenolates. It is to be noted the term normal employed hereinbefore and hereinafter denotes the ratio of the number of equivalents of calcium moiety to the number of equivalents of alkylphenol moiety is about 1, that is, the calcium metal ratio is about 1.

Although the sulfurized normal calcium alkylphenolates of the past were effective detergent-dispersants, they had the drawback of deteriorating under engine operating conditions to form undesirable oxidation products which undesirably promote corrosion and change in viscosity of lubricating oil compositions containing said sulfurized normal calcium alkylphenolate.

The prior art teaches many types of sulfurized normal calcium alkylphenolates. For example, one prior art sul- 3,528,917 Patented Sept. 15, 1970 "ice SUMMARY OF INVENTION The subject invention relates to a lubricating composition comprising a hydrocarbon oil of lubricating viscosity containing between about 0.1 and wt. percent of a novel sulfurized normal calcium alkylphenolate dispersant which is significantly less susceptible to undesirable oxidation during engine operation than many of the sul furized normal calcium alkylphenolates containing lubricant compositions of the past.

Broadly, the dispersant component is prepared by contacting in the presence of a hydrocarbon lubricating oil medium an alkylphenol, either sequentially or concur rently, with calcium alkoxyalkoxide and sulfur. Under the preferred conditions, the alkylphenol is sequentially contacted with calcium alkoxyalkoxide to form normal calcium alkylphenolate followed by a sulfur contact to form the sulfurized normal calcium alkylphenolate. Under the most preferred conditions, the calcium alkoxyalkoxide reactant in the preferred procedure is formed in the presence of the alkylphenol reactant via an alkoxyalkanol-CaC reaction at between about 0 and 250 C.

DETAILED DESCRIPTION OF THE INVENTION Specifically, the lubricating composition of the invention is prepared by contacting in the presence of a hydrocarbon lubricating oil (1) an alkylphenol of the formula:

where R represents one or two monovalent saturated aliphatic hydrocarbon radicals of from 4 to carbons and where at least one ortho or para positions remains unsubstituted, (2) a calcium alkoxyalkoxide of the formula Ca%OA-OR') where A is a divalent saturated aliphatic hydrocarbon radical (alkanediyl) of from 1 to 6 carbons and R is alkyl of from 1 to 25 carbons and (3) sulfur at a temperature between about 0 and 250 C. utilizing a mole ratio of alkylphenol to calcium alkoxyalkoxide of between about 1.8:1 and 2.2: l, preferably 2.0:l, and a mole ratio of alkylphenol to sulfur of between about 120.15 and 1:8, preferably between about 110.5 and 1:30 The sulfurized normal calcium alkylphenolate may be characterized by the following theoretical formula:

where R is as heretofore defined, x is an average integer of from about 1 to 4 and y is an average integer of from 0 to about 10. It is to be noted that x and y are defined as average integers and the foregoing formula is only set forth as a hypothetical since sulfurized normal calcium alkylphenolate is in essence a complex mixture of monosulfide and polysulfides which can be accurately defined only in terms of process. In any case, the R group is primarily in the para position with the sulfur links mainly in the ortho position. Further, there is probably also a significant amount of covalent character to the calciumoxygen bond. It is to be noted the calcium and sulfur contents of the sulfurized alkylphenolate component are respectively between about 1 and 8 wt. percent and 0.5 and 12 Wt. percent.

Under advantageous reaction conditions, the sulfur is introduced into the reaction system as a slurry in hydrocarbon lubricating oil, said slurry most preferably having a sulfur concentration of between about and 25 wt. percent. In addition, the calcium alkoxyalkoxide reactant is advantageously introduced into the reaction system as a solution if not already a liquid to facilitate reactant contact. The solvent medium is desirably the corresponding alkoxyalkanol (if liquid) of the alkoxyalkoxide component. The concentration of the calcium alkoxyal-koxide in said solvent medium is advantageously between about 20 and 60 wt. percent.

Under preferred reaction conditions the alkylphenol in the first stage is contacted with the calcium alkoxyalkoxide at a temperature between about 0 and 250 C. for a period of time, e.g., between 0.01 and 15 hours to form calcium alkylphenolate characterized by the formula:

where R is as heretofore defined. A hydrocarbon lubricating oil reaction medium is desirably employed in the first stage of the reaction and is carried along through the entire reaction and forms a part of the final lubricating oil composition. The hydrocarbon lubricating oil is most preferably employed in an amount so that it will constitute between about 15 and 70% of the first stage reaction mixture after removal of volatile unreacted materials.

Under the most preferred conditions the calcium alkoxyalkoxide reactant is prepared in the situs of the first stage contacting. This is accomplished by introducing into the first stage under the aforementioned first stage conditions calcium carbide and alkoxyalkanol of the formula where R and A are as heretofore defined in a mole ratio of CaC to R'OAOH of between about 1:2 and 1:50. The calcium carbide and alkoxyalkanol react to form the calcium alkoxyalkoxide which in turn reacts with the alkylphenol to form the calcium alkylphenolate. Since the reactivity of the CaC is an inverse function of its particle size the employment of finely divided, particularly powdered CaC is desirable. The most preferred conditions permit the method of preparation to be carried out in a single reactor which results in a material saving in required process equipment and expense.

Prior to the next stage of the preferred reaction, the alkoxyalkanol, if present, is desirably removed from the reaction mixture, e.g., by standard means such as stripping with an inert gas (e.g. nitrogen) under conditions of distillation therefor: The purpose of removing the alkoxyalkanol prior tocontacting with sulfur is to prevent sulfur contamination of the alkoxyalkanol. Sulfur contamination of the alkoxyalkanol reduces its desirability for further use.

As a next step in the preferred procedure, to the stripped or unstripped reaction mixture of the first stage there is lubricating oil composition containing between about 0.1 and sulfurized normal calcium alkylphenolate having a calcium metal ratio of about 1, said composition having sulfur content between about .01 and 11 wt. percent and calcium content between about .01 and 7 wt. percent.

Advantageously, under the preferred procedure the formed lubricating oil composition is blown with carbon dioxide, preferably bracketed by inert gas stripping. The carbon dioxide treatment functions to deodorize the product concentrate. In addition to deodorization, the carbon dioxide appears to somewhat improve the filterability and stability of the concentrate product. The inert and CO stripping rates generally employed is between about 0.1 and 10 s.c.f.h./ gallon of reaction mixture and is conducted at between about 10 and 250 C.

If desired, the formed product may be further purified by standard means such as filtration to remove any noncolloidal solid bodies.

In the aforedescribed procedure for the manufacture of the sulfurized normal calcium alkylphenolate lubricant compositions the reason it is desirable to first form the calcium alkylphenolate prior to sulfurization or at least simultaneously with sulfurization as alkylphenols sulfurize less readily than their calcium alkylphenolate counterparts. Further, in the foregoing procedure the reactions are conducted most preferably in an inert gas atmosphere and under conditions of agitation.

As heretofore stated, the sulfurized normal calcium alkylphenolate contents in the lubricating oil composition of the invention may range anywhere from 0.1 to 90 Wt. percent. The higher concentrations, e.g., between about 10 and 90 wt. percent, sometimes referred to in the art as concentrates, are normally found in lubricant compositions resulting directly from the manufacture of the sulfurized normal calcium alkylphenolate whereas the preferred sulfurized alkylphenolate concentration in lubricating oil compositions employed for automotive use is between about 0.5 to 5 wt. percent. In any case, in the entire percent range the additive in the lubricating compositions of the invention will function as a detergent-dispersant and the resultant compositions will have at least some lubricating function.

It is to be noted in the finished lubricating oil composition other additives may be included, these other additives may be any of the standard suitable pour depressors, additional sludge dispersants (e.g., petroleum sulfonates), antioxidants, silver corrosion inhibitors, viscosity index improvers, oiliness agents and mixtures thereof. Exactly what other additives are included in the finished oil and the particular amounts therein will, of course, depend on the particular use conditions desired for the finished ,oil product.

Suitable base oils useful in the composition of the invention as well as diluent in the manufacture of the sulfurized normal calcium alkylphenolate lubricating oil concentrate include a wide variety of hydrocarbon lubricating oils such as naphthenic base, paraffin base and mixed base mineral oils or other hydrocarbon lubricant, e.g. lubricating oils derived from coal products and synthetic hydrocarbon oils, e.g., alkylene polymers such as polypropylene and polyisobutylene of a molecular weight between about 250 and 2500. Advantageously, the lubricating base oils having an SUS viscosity at F. between about 50 and 2000 are employed.

Specific examples of the alkylphenol reactants contemplated herein are 4-octylphenol, 4-tertiary octylphenol, Z-decylphenol, 2-dodecylphenol, 4-hexadecylphenol, 2,4- didodecylphenol, 2-nonylphenol, 4-tricontylphenol, 4-eicosylphenol, a mixture of decylphenol and dodecylphenol (C -C alkylphenol) and mixtures of 2 and 4 positioned monalkyl and dialkylphenols. It is to be noted the alkylphenols employed will normally be para alkylphenols, however, 2,4-substituted dialkylphenols may also be employed. The only restriction is at least one ortho or para position of the alkylphenol reactant is desirably available for sulfurization.

Examples of the calcium alkoxyalkoxide reactants contemplated herein are calcium 2-methoxyethoxide, calcium l-methoxypropoxide, calcium 3-methoxybutoxide, calcium 2-ethoxyethoxide and calcium 4-dodecoxyhexoxide.

Examples of the alkoxyalkanols contemplated herein are Z-methoxyethanol, l-methoxypropanol, 3-methoxy butanol, 2-ethoxyethanol and dodecoxyhexanol.

Specific examples of the sulfurized normal calcium alkylphenolate component expressed in terms of the theo retical formula area are where R is 4-octyl, x is 1 and y is R is 4-dodecyl, x is 1 and y is 1; R is 4-eicosyl, x is 3 and y is R is 2,4-didecyl, x is 2 and y is 3; and mixtures thereof. It is to be noted x and y are set forth as average integers.

The following examples further illustrate the invention but are not to be construed as limitations thereof.

Example I.This example illustrates the preparation of the sulfurized normal calcium alkylphenolate and the lubricant composition resulting therefrom.

To a 50 gallon reactor fitted with a variable speed stirrer and means for heating, collecting volatile overhead and purging with gas, there was charged 124 lbs. (0.42 mole) of 4-C C alkylphenol and 120 lbs. of paraflinic base lubricating oil having an SUS viscosity at 100 F. of about 100. The resultant mixture was heated from ambient to 165 C. over a period of two hours while passing nitrogen therethrough at a rate of 0.1 s.c.f.h./lb. mixture. At this point, 106 lbs. (0.21 mole) of 38 wt. percent calcium Z-methoxyethoxide in ethoxyethanol were added and the temperature and nitrogen flowing was continued over a period of an additional 2.5 hours while distilling off methoxyethanol solvent and by-products. At the end of the 2.5 hour period there was charged to the residue 16.8 lbs. (0.525 mole) of a 46 Wt. percent sulfur in lubricating oil slurry, said lubricating oil having an SUS viscosity of about 100 at 100 F. and the temperature was raised to and maintained at 180 C. for a period of 4 hours with nitrogen flowing continuing at a rate of 0.1 s.c.f.h./lbs. Then for deodorization 6 lbs. of carbon dioxide were blown through the reaction mixture over a A hour period followed by nitrogen blowing at 0.4 s.c.f.h./lb. for 1 hour, the stripped mixture was filtered through a pressure filter at 140 C. under 10 p.s.i. pressure utilizing 2.8 lbs. diatomaceous filter aid. The recovered filtrate (280 lbs.) gave the following analysis:

TABLE I Test: Results Calcium, wt. percent 2.95 Sulfur, wt. percent 2.7 TBN (HClO titration) 1.4

Sp. grav. 60/60 0.9715

Viscosity, SUS 210 F 127 Flashpoint, F. 360 Sulfated ash, wt. percent ponent contemplated herein and the lubricating compositions resulting therefrom.

To a 2 liter reactor fitted with a variable speed stirrer and means for heating, collecting volatile overhead and purging with gases there was charged 295 grams (1 mole) of 4-C C alkylphenol, 254 grams (0.5 mole) of a 39 wt. percent of calcium 2-methoxyethoxide in methoxyethanol and 322 grams of paraifinic base lubricating oil having an S'US viscosity at F. of about 100. The resultant mixture was heated from ambient to about C. over a period of 0.75 hour While passing nitrogen therethrough at a rate of 0.1 s.c.f.h./lb. mixture and 134 mls. of methoxyethanol (60%) were collected as overhead. At the end of the 0.75 hour period there was charged to the residue 16 grams (0.5 mole) sulfur and the temperature was raised to and maintained at C. for a 5 hour period with nitrogen blowing continuing at a rate of 2001000 mls./min. At the end of the 5 hour period the mixture was filtered at 180 C. utilizing about 25 grams of diatomaceous filter aid. The receovered filtrate (614 grams) gave the following analysis:

TABLE II Tests: Results Calcium, wt. percent 2.8 Sulfur, Wt. percent 1.6 TBN (HC1O titration) 82.3 Kin. visc., cs., 40 F. 21.3

1 Total base number.

The filtrate was determined to be a lubricating oil solution containing 50 wt. percent sulfurized normal calcium 4-C -C alkylphenolate having a calcium metal ratio of about 1.

Example IIl.- This example still further illustrates the preparation of the sulfurized normal calcium alkylphenolate component contemplated herein.

A 3000 ml. flask was charged with 400 g. (1.0 mole) of a 4-C (average) polybutenephenol, 440 g. of hydrocarbon diluent oil (100 SUS/100 F.), 402 g. (1.65 mole) sulfur and 299 g. (0.5 mole) of a 32 wt. percent solution of calcium 2-methoxyethoxide in 2-methoxyethanol. The mixture was stripped of Z-methoxyethanol by heating to 180 C. with stirring and an N purge. The

mixture was maintained under these conditions for a five hour period then treated with C0 (500 mL/min.) for 15 minutes and was filtered hot under mild vacuum through a bed of diatomaceous filter aid. The filtrate was analyzed and found to be a 858 g. lube oil composition containing sulfurized normal calcium 4-C (average) polyisobutenephenolate having a calcium metal ratio of about 1, said composition containing 2 wt. percent Ca and 2.3 wt. percent sulfur.

Example I V.This example illustrates the method of the invention utilizing in situ formed calcium alkoxyalkoxide as reactant.

To a 12 liter reactor fitted with a variable speed stirrer and means for heating, collecting volatile overhead and purging with gases there was charged 1530 g. (5.0 mole) of 4-C C alkylphenol, 1000 mls. Z-methoxyethanol, and 1630 g. of paraffinic base lubricating oil having an SUS viscosity at 1000 F. of about 100. The resultant mixture was heated to reflux While passing nitrogen therethrough at a rate of 100 ml./min, To this refluxing mixture was added 200 g. (3.125 mole) calcium carbide over a period of one-half hour. The refluxing under a nitrogen cover was continued a further 3 hours and the refluxed mixture was then stripped with N at 500 ml./min. to 177 C. (350 F.). When temperature was reached, 200 g. (6.25 mole) sulfur was added and the mixture CO blown at 1500 ml./min. for 6 hours. It was then N blown at 2000 ml./min. for 1 hour (92% solvent was recovered) and filtered through diatomaceous filter aid. The recovered filtrate (3238 g.) was determined to be a lubricating oil composition containing sulfurized normal calcium 4-C C alkylphenolate of a calcium metal ratio of about 1 giving the following analysis:

TABLE III Test: Found Calcium, wt. percent 2.8 Sulfur, Wt. percent 3.4 TBN (HClO 97.3 Flashpoint, F. 375 Kin. visc., 210 F., cs. 23.9

Example V.This example illustrates the superiority of the sulfurized normal calcium alkylphenolate of the invention in respect to resistance to undesirable oxidation. As a corrollary such a showing illustrates the material difrerence in composition of the sulfurized normal calcium alkylphenolates of the invention in regard to those of the past.

Four lubricant compositions were tested in three subsequently described tests. Composition A is a final filtrate product composition of Example I. Compositions B, C and D are comparative compositions containing sulfurized normal calcium alkylphenolate prepared by a procedure other than that of the invention.

Comparative Composition B was prepared by the following procedure:

To a 12 liter reactor fitted with a variable speed stirrer and means for heating, collecting volatile overhead and purging with gases there was charged 2142 grams (7.0 mole) 4-C C alkylphenol, 280 grams (8.75 mole) of powdered sulfur, 2268 grams paraffinic lubricating oil of an SUS viscosity at 100 F. of about 100, 315 grams (4.06 mole) calcium hydroxide and 224 grams (3.5 mole) of ethylene glycol. The stirrer was activated and nitrogen was passed through the reaction mixture during the entire reaction at a rate of 1000 ml./min. mixture. The reaction mixture was heated to 145 C. over a period of about an hour and held there for an additional 3 hours. Toluene in an amount of 1050 g. was added. The result ant mixture was heated to reflux and H O-glycol azeotroped off while toluene was recycled. When no more H O-glycol azeotroped out, toluene was stripped and the temperature was raised to 177 C. The product was stirred at 177 C. with CO at 1000 ml./min. for 3 hours. The resultant product was filtered at 150 C. through a bed of diatomaceous earth. The recovered filtrate designated as Composition B was determined to be a lubricating oil solution containing sulfurized normal calcium 4-C C alkylphenolate of a calcium metal ratio of about 1. Compositions C and D were prepared by the same general procedure as Composition B except for the following exceptions:

(1) In the preparation of Composition C 326 g. (5.25 m.) ethylene glycol and 180 g. (5.63 In.) sulfur Were used.

(2) Composition D was Composition C re-sulfurized with an additional 85 g. (2.66 m.) sulfur at 177 C. for

2 hours. Then 400 mls. of toluene were added, and the mixture was refluxed overnight, stripped with N (1000 mls./min.) to 177 C., stirred 1 hour at 177 C. with CO blowing (1000 mls./min.) and filtered.

Compositions C and D were both determined to contain sulfurized normal calcium 4-C -C alkylphenolate having a calcium metal ratio of about 1.

Compositions A, B, C and D were analyzed and the following was found:

TABLE IV Compositions Tests A B C D Calcium, wt. percent 2.95 2 5 2.8 2.8 Calcium metal ratio 1 1 1 1 Sulfur, wt. percent-.. 2. 7 3 1. 9 2. 4 Diluent oil, wt. percent 50 50 50 50 TBN (H0104 titration) 1. 4 Sp. grav. 60/60 0.9715 visc., SUS, 210 F 127 Also included in the above four blends in an amount constituting 5.0 wt. percent (0.05 wt. percent P) of an ethoxylated derivative of polyisobutene (1100 m.w.) thiophosphonic acid.

For the subsequent described tests Composition A and Comparative Compositions B, C and D were diluted with additional paraffinic lubricating oil until sulfurized normal calcium alkylphenolate content in each was 0.20 wt. percent.

A description of the tests employed is as follows:

(a) EMD viscosity change test.-In this test 300 ml. of the test sample of oil are stirred at 300 r.p.m. for a period of 72 hours at 285 F. Silver and copper metal strips are present. The run is again repeated with a new test sample of oil at 325 F. The SUS viscosity at 100 F. of the test oil is measured before and after test and the percentage change viscosity is calculated. The greater the percent change the greater the oxidative deterioration of the blend containing the sulfurized normal calcium alkylphenolate component.

(b) Modified G.E. oxidation test-This test comprises stirring 800 mls. of test oil composition at 330 r.p.m. for a 48 hour period at 300 F. The viscosity in terms of kin. visc., cs. at 100 F. is measured before and after the test. The percent viscosity increase is directly proportional to the extent of undesirable oxidative deterioration of the test blend.

(c) Lead strip corrosion test-The test consists of exposing a lead specimen to the action of the test lubricating oil sample for 1 hour at 325 F. 12 F. in the presence of copper catalyst. The test lubricant is mechanically stirred and filtered, dry air is introduced into the test lubricant at a controlled rate. The results are presented as change in weight milligrams (mgs.) per square inch of lead specimen surface area. The greater the weight loss the greater the oxidative deterioration of the blended oil containing the sulfurized normal calcium alkylphenolate component.

(d) Railway diesel oil (RDO) spray deposition test.- An aluminum panel heated to 600 F. is sprayed with the test blend maintained at 325 F. through a fuel nozzle at 2 gal/hour for an egiht hour period. The panel is then cooled, rinsed with pentane, and visually rated for deposits (0=clean, =heavy carbon). The averaged deposit condition gives the rating, the lowest number representing the cleanest conditions and this is related to the tendency of the lubricant to undergo oxidative-thermal degradation under high temperature thin film conditions. The ratings are also proportional to the piston demerit ratings in actual diesel engine testing. This test is also a detergency test.

The diluted blends of the aforedescribed representative composition A and comparative compositions B, C, and D were subjected to the foregoing tests and the results are reported below in Table V:

TABLE V Dilute Tests A B O D EMD, 72 hrs. 285 F., percent vis. inc 19 118 23 325 F. percent vis. increase 24 88 44 48 GE oxidation test, percent vise. increase- 1 15 22 13 Lead strip corrosion test, mg. wt. loss-.- 87 109 154 124 RDO test, demerits 5 25 33 1 Average.

is described in FTMS 791a-346T and Caterpillar Information Letter No. 46. Performance of the test lubricant is judged by examination of the piston after 480 hours of engine operation for percent coverage by lacquer and percent of the groove filled with coke. The higher the percent the less elfective the lubricating oil composition from a detergent aspect.

Composition X is tested and consisted of a parafiinic lubricating base oil containing the additives sulfurized calcium 4-C C alkylphenolate of the type produced in Example I and an ethoxylated derivative of polyisobutene (1100 M.W.) thiophosphoric acid, said additives being present in quantities to give the test oil composition a calcium content of 0.19% and a phosphorus content of .05 wt. percent. Comparative Composition Y is also tested and is similar to Composition X but the sulfurized calcium 4-C C alkylphenolate is deleted.

The test results at the end of 480 hours find Com position X passed the detergency requirement of military specification MIL 2104B whereas Composition Y failed said requirement.

We claim:

1. A lubricating oil composition comprising a hydrocarbon oil of lubricating viscosity containing between about 0.1 and 90 wt. percent of a snlfurized normal calcium alkylphenolate, said alkylphenolate having a calcium metal ratio of about 1, a calcium content of between about 1 and 8 wt. percent and a sulfur content between about 0.5 and 12 wt. percent, wherein said sulfurized calcium alkylphenolate is produced by contacting in a hydrocarbon lubricating oil medium (1) alkylphenol of the formula:

where R is alkyl of from 4 to 100 carbons (2) sulfur, and (3) calcium alkoxyalkoxide of the formula CatC-A-OR 2 where A is alkanediyl of from 1 to 6 carbons and R is alkyl of from 1 to 25 carbons, at a temperature between about 0 and 250 C. utilizing a mole ratio of said alkylphenol to sulfur of between about 12015 and 1:8 and alkylphenol to calcium alkoxyalkoxide of between about 1.821 and 2.221.

2. A lubricating oil composition comprising a hydrocarbon oil of lubricating viscosity containing between about 0.1 and 90 Wt. percent of sulfurized normal calcium alkylphenolate, said alkylphenolate having a calcium metal ratio of about 1, a calcium content between about 1 and 8 wt. percent and a sulfur content of between about 0.5 and 12 wt. percent, wherein said sulfurized calcium alkylphenolate is produced by first contacting in a hydrocarbon lubricating oil medium an alkylphenol of the formula:

where R is alkyl of from 4 to 100 carbons with calcium alkoxyalkoxide of the formula Ca{-OA-0R) where A is alkanediyl of from 1 to 6 carbons and R is alkyl of from 1 to 25 carbons at a temperature between about 0 and 250 C. in a mole ratio of said alkylphenol to said calcium alkoxyalkoxide of between about 1.821 and 22:1 to form a calcium alkylphenolate, then second contacting said formed calcium alkylphenolate with sulfur at a temperature between about 0 and 250 C. in a mole ratio of said alkylphenol to said sulfur of between about 1:015 and 1.8 thereby forming a resultant mixture of said hydrocarbon oil and said sulfurized normal calcium alkylphenolate.

3. A lubricating oil composition in accordance with claim 2 wherein said resultant mixture is further contacted with carbon dioxide at a temperature between about 10 and 250 C. utilizing carbon dioxide at a rate of between about 0.1 and 10 s.c.f.h./gallon of said mixture.

4. A lubricating oil composition in accordance with claim 2 wherein said alkylphenol is 4-C C alkylphenol, said calcium alkoxyalkoxide is calcium Z-methoxyethoxide, and said calcium alkylphenolate is calcium 4-C -C alkylphenolate.

5. A lubricating oil composition in accordance with claim 2 wherein said first and second contacting is conducted in an inert gas atmosphere, said calcium alkoxyalkoxide is introduced as between about 20 and 60 wt. percent solution in inert volatile solvent and said solvent and volatile by-products are removed prior to said seconcl contacting, wherein in said second contacting said sulfur is introduced as between about 10 and 25 wt. percent slurry in hydrocarbon lubricating oil and said resultant mixture is sequentially blown with inert gas, carbon dioxide, and inert gas at a temperature between about 10 and 250 C.

6. A lubricating oil composition in accordance with claim 5 wherein said alkylphenol is 4-C -C alkylphenol, said calcium alkoxyalkoxide is calcium Z-methoxyethoxide, said solvent is 2-methoxyethanol, and said inert gas is nitrogen.

7. A oil composition in accordance with claim 2 wherein said calcium alkoxyalkoxide is formed in the presence of said alkylphenol and said hydrocarbon lubricating oil medium, the preparation comprising contacting calcium carbide with alkoxyalkanol of the formula RO-AOH where R and A are as heretofore defined at a temperature between about 0 and 250 C. utilizing a mole ratio of CaC to R'OAOH of between about 1:2 and 1:50.

8. A oil composition in accordance with claim 7 wherein said first and second contacting is conducted in an inert gas atmosphere, and volatile by-products and unreacted initial ingredients are removed prior to said second contacting via inert gas blowing and herein subsequent to said second contacting the resultant mixture is sequentially blown with inert gas, carbon dioxide and inert gas.

9. A oil composition in accordance with claim 7 wherein said alkylphenol is 4-C C alkylphenol, said alkoxyalkanol is Z-methoxyalkanol, said calcium alkoxyalkoxide is calcium Z-methoxyethoxide, and said sulfurized calcium alkylphenolate is sulfurized calcium 4-C C alkylphenolate.

References Cited UNITED STATES PATENTS 2,680,096 3/1954 Walker et al. 25242.7 2,870,134 1/1959 Kluge et al. 25242.7 X 2,916,454 12/1959 Bradley et al. 25242.7 3,150,088 12/1964 Hunt et al. 25218 X 3,425,941 2/ 1969 Kivelevich 25242.7

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R.