US3761414A

US3761414A - Sulfurized calcium alkylphenolate lubricants

Info

Publication number: US3761414A
Application number: US00180829A
Authority: US
Inventors: H Haugen; H Chafetz
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1971-09-15
Filing date: 1971-09-15
Publication date: 1973-09-25
Anticipated expiration: 1990-09-25
Also published as: AU472816B2; SE384034B; DE2335519A1; BE802696A; NL7309981A; FR2238702B1; JPS5028504A; AU5797573A; CA979423A; SE7309804L; FR2238702A1; GB1377320A

Abstract

A LUBRICATING OIL COMPOSITION CONTAINING SULFURIZED NORMAL CALCIUM ALKYLPHENOLATE DETERGENT DISPERSANT OF IMPROVED ANTICORROSIVE PROPERTIES AND RESISTANCE TO OXIDATION, SAID DISPERSANT PREPARED BY A THREE-STEP PROCEDURE COMPRISING (1) REACTING AT A TEMPERATURE BETWEEN ABOUT 200 AND 425* F. IN THE PRESENCE OF A HYDROCARBON LUBRICATING OIL AN ALKYLPHENOL WITH A FIRST ADDITION OF CALCIUM ALKOXYALKOXIDE UTILIZING BETWEEN ABOUT 45 AND 90 WT. PERCENT OF THE STOICHIOMETRIC AMOUNT REQUIRED TO CONVERT THE ALKYLPHENOL TO CALCIUM ALKYLPHENOLATE, (2) CONTACTING AT A TEMPERATURE BETWEEN ABOUT 350 AND 425*F. THE RESULTANT REACTION MIXTURE WITH SULFUR UTILIZING A MOLE RATIO OF SULFURTO INITIAL ALKYLPHENOL OF BETWEEN ABOUT 0.5:1 AND 8:1 WHILE PASSING AN INERT GAS THROUGH THE REACTION MIXTURE AT A RATE OF BETWEEN ABOUT 0.1 AND 10 S.C.F.H./GALLON AT BETWEEN ABOUT 350 AND 425*F. UNTIL HYDROGEN SULFIDE CONTENT OF LESS THAN ABOUT 3 P.P.M. IS OBTAINED, (3) REACTING THE BLOWN MIXTURE WITH A SECOND ADDITION OF CALCIUM ALKOXYALKOXIDE AT A TEMPERATURE OF BETWEEN ABOUT 350 AND 425*F., SAID FIRST AND SECOND ADDITION TOTALING BETWEEN ABOUT 100 AND 120% OF THE STOICHIOMETRIC AMOUNT OF CALCIUM ALKOXYALKOXIDE TO FORM SAID CALCIUM ALKYLPHENOLATE, SAID COMPOSITION PREFERABLY CONTAINING A SUPPLEMENTARY DETERGENT DISPERSANT COMPRISING AN ETHYLENE OXIDE DERIVTIVE OF AN INORGANIC PHOSPHORUS ACID FREE, STEAM HYDROLYZED, POLYBUTENE-P2S5 REACTION PRODUCT.

Description

United States Patent 3,761,414 SULFURIZED CALCIUM ALKYLPHENOLATE LUBRICANTS Haakon Haugen, Beacon, and Harry Chafetz, Poughkeepsie, N.Y., assignors to Texaco line, New York,

Nb Drawing. Filed Sept. 15, 1971, Ser. No. 180,829 rm. c1. C10m 1/20 US. Cl. 252-4237 6 Claims ABSTRACT OF THE DISCLOSURE A lubricating oil composition containing sulfurized normal calcium alkylphenolate detergent dispersant of improved anticorrosive properties and resistance to oxidation, said dispersant prepared by a three-step procedure comprising 1) reacting at a temperature between about 200 and 425 F. in the presence of a hydrocarbon lubricating oil an alkylphenol with a first addition of calcium alkoxyalkoxide utilizing between about 45 and 90 wt. percent of the stoichiometric amount required to convert the alkylphenol to calcium alkylphenolate, (2) contacting at a temperature between about 350 and 425 F. the resultant reaction mixture with sulfur utilizing a mole ratio of sulfur to initial alkylphenol of between about 05:1 and 8:1 while passing an inert gas through the reaction mixture at a rate of between about 0.1 and 10 s.c.f.h./gallon at between about 350 and 425 F. until hydrogen sulfide content of less than about 3 p.p.m. is obtained, (3) reacting the blown mixture with a second addition of calcium alkoxyalkoxide at a temperature of between about 350 and 425 F., said first and second addition totaling between about 100 and 120% of the stoichiometric amount of calcium alkoxyalkoxide to form said calcium alkylphenolate, said composition preferably containing a supplementary detergent dispersant comprising an ethylene oxide derivative of an inorganic phosphorus acid free, steam hydrolyzed, polybutene-P S reaction product.

BACKGROUND OF THE INVENTION This invention is in the field of art relating to fluid compositions particularly designed for use between two relatively moving surfaces to reduce the friction therebetween and to preserve the surface. The lubricant compositions of the invention contain a compound which has a calcium component linked to a carbon through oxygen and preferably containing in addition thereto a detergent dispersant for lube oil composed of carbon, hydrogen, oxygen, phosphorus and sulfur.

Lubricating oils subjected to severe stress such as railway diesel engine lubricating oils readily deteriorate under such conditions with attendant formation of sludge, lacquer, resinous materials which adhere to the engine parts, particularly the piston ring groove, thereby lowering the operating efficiency of the engine. To counteract the formation of these deposits, certain chemical additives have been found which 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 efficient operating condition for extended periods of time. These agents are known in the art as detergents and/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 calcium sulfurized normal alkylphenolates. It is to be noted that the term normal employed hereinbefore and hereinafter denotes the ratio of the number of equivalents of calcium moiety, the number of equivalents of alkylphenol moiety is about 1, that is, the calcium ratio is about 1.

Althoughv the sulfurized normal calcium alkylpheno- 3,761,414 Patented Sept. 25, 1973 lates of the past were effective detergent dispersants, they were found to be somewhat less than satisfactory in respect to their corrosivity to copper-lead and lead bearings under operating conditions and further under severe conditions, such as in diesel engine operations, forming oxidation products which undesirably result in a substantial change in lubricant viscosity. In an effort to solve this problem, improved sulfurized calcium alkylphenolate lubricant compositions were formulated as covered in US. Pats. Nos. 3,528,917 and 3,549,534. However, with antipollution devices subjecting lubricating oils to even more severe conditions, a sulfurized normal calcium alkylphenolate of even still further reduced corrosivity to bearings and resistance to undesirable oxidation in engine operating conditions was required.

SUMMARY OF THE INVENTION We have discovered and this constitutes our invention a further improved sulfurized normal calcium alkylphenolate lubricant compositions which are substantially less susceptible to undesired oxidation'during engine operating and substantially less corrosive to the metal engine parts such as lead and copper-lead bearings than the sulfurized normal calcium alkylphenolates heretofore known. More specifically, we have unexpectedly discovered in the manufacture of the compositions that by bracketing the sulfurization step with calcium alkoxyalkoxide additions utilizing between about 45 and of the required stoichiometric amount in the first addition prior to sulfurization and then adding sufficient calcium alkoxyalkoxide in-the second addition subsequent to sulfurization in a sufficient amount to be about to of stoichiometric, a lubricant composition is formed which substantially reduces engine bearing wear and is substantially more resistant to oxidation as measured by change in the lubricating oil viscosity after being subjected to severe engine conditions. V DETAILED DESCRIPTION OF THE INVENTION Specifically, the lubricating composition of the invention is prepared by a three-stage procedure:

In the first stage, in the presence of a lubricating oil, there is contacted (1) an alkylphenol of the formula:

where A is a divalent saturated aliphatic hydrocarbon radical (alkanediyl) of 1 to 6 carbons and R is alkyl of from 1 to 25 carbons at a temperature between about 200 and 425 F., preferably between about 320 and 425 F., utilizing a mole ratio of calcium alkoxyalkoxide to alkylphenol of between about 0.225 :1 and 0.45:1, that is, an amount of a calcium alkoxyalkoxide of between about 45 and 90 wt. percent of stoichiometric. The reaction period is conducted until essentially all the alkoxyalkoxide has reacted which is generally between about 0.5 and 8 hours.

As a second stage, contacting the resultant first mixture with sulfur at a temperature between about 350 and 425 F., preferably between about 400 and 425 F., utilizing a mole ratio of sulfur to initial alkylphenol of between about 0.5 :1 and 8:1, preferably between about 0.5 :1 and 3, to form a second reaction mixture while passing through the second reaction mixture inert gas, preferably utilizing a sequential inert gas. carbon dioxide,

inert gas blowing until no detectable H S odor is found which is normally measured at less than 3 p.p.m. H 8 and a copper strip corrosion (ASTM D130) of 2A maximum (3 hrs-212 F.). A gas rate of between about 0.1 to 10 s.c.f.h./ gallon is advantageously employed. The carbon dioxide functions as a deodorizing agent whereas the iner gas blowing until no detectable H 8 odor is found tiles. The total reaction time in the second stage generally ranges between about 0.5 and 10 hours.

Then as a third stage, contacting the gas blown second reaction mixture with a second amount of calcium alkoxyalkoxide at a temperature between about 350 and 425 F., preferably between about 400 and 425 F., utilizing between about 0.15 and 0.375 mole of calcium alkoxyalkoxide per mole of original alkylphenol, the first and second additions totaling between about 100% and 120% of stoichiometric. The third stage reaction time is generally between about 0.5 and 8 hours.

All three stages of the reaction are preferably conducted in the presence of a hydrocarbon lubricating oil medium which is also suitable to function to form a portion of the base oil in the final compositions containing the sulfurized normal calcium alkylphenolate. Suitable base oils and diluent oils include a wide variety of hydrocarbon lubricating oils such as naphthenic base, parafiinic base and mixed naphthenic and paraffinic base oils having an SUS viscosity at 100 F. of between about 50 and 2500, preferably between about 90 and 150. In formulating the diesel lubricating oil compositions, the finished compositions desirably have an SUS viscosity between about 900 and 1100 at 100 F. In the three stages the diluent oil normally constitutes between about 25 and 80 wt. percent of the reaction mixture.

Under advantageous conditions in the first and third stages, the calcium alkoxyalkoxide reactant is introduced into the reaction system as a solution if not already in liquid form to facilitate reactant contact. The solvent medium is usually the corresponding alkoxyalkanol (if liquid) of the alkoxyalkoxide component. The concentration of the calcium alkoxyalkoxide in the solvent medium is advantageously between about 20 and 60 wt. percent. The solvent is normally removed as overhead during the early phase of each stage.

In the second sulfurization stage, the sulfur is desirably introduced as a slurry in a hydrocarbon lubricating oil, such slurry most preferably having a sulfur content between about 10 and 25 wt. percent. The lubricating oil as in all the stages continues on and makes up a portion of the final concentrate product.

In addition to the second stage, the first and third stage reactions are preferably conducted in an inert gas atmosphere, e.g., employing inert gas blowing (0.1-10 s.c.f.h./ gallon). Further, agitation is normally employed in all three stages of the procedure in order to facilitate ingredient content.

The final product is advantageously filtered, if desired, by standard means. The preferred filtration is accomplished by adding to the final reaction mixture between about 0.01 and 1 wt. percent diatornaceous earth and passing material to be filtered through press leaf filter precoated with diatornaceous earth at a temperature between about 200 and 300 F. and a pressure between about and 100 p.s.i.g.

The formed sulfurized normal calcium alkylphenolate product contents in the lubricating oil compositions contemplated herein range anywhere from 0.1 to 90 wt. percent. The higher concentrations, e.g., between about 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 sulfurized calcium alkylphenolate ingredients in finished (dilute) lubricating oil compositions employed for engine use is desirably between about 0.1 and 7.5 wt. percent with a calcium concentration of between about 0.06 and 0.5 wt. percent, preferably between about 0.1 and 0.4 wt. percent. In any case, the entire percent range of the additive in the lubricating composition will function as a detergent-dispersant and the resultant composition will at least have some lubricating function.

In the finished lubricating oil compositions, other additives may be included such as pour depressors, antioxidants, silver corrosion inhibitors, viscosity index improvers, oleogeneous 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 the finished oil product is to be put to. One of the most suitable uses found for the sulfurized normal calcium alkylphenolate produced herein are lubricants for railway diesel engines. When this is the case, it is desirable to include in the oil in addition to the aforedescribed sulfurized calcium alkylphenolate, ethoxylated inorganic phosphorus acid free, steam hydrolyzed, polybutene-P S reaction products further described in US. Pats. Nos. 3,272,744 and 3,087,956. This supplementary detergent appears to cooperate with the subject sulfurized normal calcium alkylphenolate to enhance detergency and thermal stability and resistance to undesired oxidative decomposition. The ethoxylated product is present in the finished compositions of the invention in amounts between about 0.3 and 6 wt. percent (oil free basis), preferably between about 0.8 and 4 wt. percent, and in any case, in sufficient amount to give a phosphorus content in the finished (dilute) composition of between about 0.006 and 0.15 wt. percent, preferably between about 0.01 and 0.08 wt. percent. The sulfurized calcium alkylphenolate ethoxylated polybutene-P S containing finished formulations are normally prepared by blending a Inbricating oil concentration of the sulfurized alkylphenolate in a lubricating oil concentrate of the ethoxylated polybutene-P S reaction product and then diluting the resultant mixture with additional hydrocarbon lubricating oil until the desired concentration of the additive is ob tained. A most-preferred finished composition contains both additives wherein the calcium content is between about 0.01 and 0.4 wt. percent, and a phosphorus content between about 0.05 and 0.08 wt. percent.

Specific examples of the alkylphenol reactants contemplated herein are 4 octylphenol, 4-t-octylphenol, 2- decylphenol, Z-dodecylphenol, 4-hexadecylphenol, 3,4- didodecylphenol, 2-nonylphenol, 4-tricontylphenol, 4- eicosylphenol and a mixture of decyl and dodecyl phenol (Q +C alkylphenol) and a mixture of 2 and 4 posit1oned monoalkyl and dialkylphenols. It is to be noted that the alkylphenols employed will normally be p-alkylphenols, however, 2,4-substituted alkylphenols may also be employed. The only restriction is l-ortho or para positions of the alkylphenol reactant is desirably available for sulfurization.

Examples of the calcium alkoxyalkoxide reactants contemplated herein are calcium Z-methoxyethoxide, calcium 2-methoxypropoxide, calcium 3-methoxybutoxide, calcium 2-ethoxyethoxide and calcium 4-dodecoxyhexoxide. Their corresponding alkoxyethanol diluents are 2- methoxyethanol, Z-methoxypropanol, S-methoxybutanol, 2-ethoxyethanol and 4-dodecoxyhexanol.

The inert gas normally employed is nitrogen and, most preferably, nitrogen with a purity of at least about 99 wt. percent.

The sulfurized normal calcium alkylphenolates are in actually a complex mixture of many compounds. One hypothetical representation employed in the art is as follows:

O- l l {Q (1 y/2) Ca where R is as" heretofore defined, x is an integer from about 1 to 4 and y is an average integer of from to 10. The foregoing formula is only set forth as a visual representation since sulfurized normal calcium alkylphenolate is; in essence a complex mixture of many substances including mono and poly sulfides, and therefore, the product can only be truly defined only in terms of process. In any case, the R group is believed to be primarily in the para position and the sulfur linked mainly in the ortho position. Further, there is probably also a significant amount of covalent character for the calciumoxygen bond. It is to be noted that the calcium and sulfur contents of the sulfurized calcium alkylphenolate component are respectively between about 1 and 8 wt. percent and 0.5 and 12 wt. percent.

Asto the alternatively included ethoxylated derivative of inorganic phosphorus acid free, steam hydrolyzed polybutene-P 8 reaction product, it is prepared by first reacting a polybutadiene of a molecular weight of between about 800 and 2500 wherein the reaction constitutes between about 5 and 40 wt. percent P 8 at an elevated temperature of between about 212 and 600 F. in a non-oxidizing atmosphere, e.g., nitrogen followed by hydrolyzing the resultant product by contacting with steam at af temperature between about 212 and 500 F. The steam treatment of the P S -polybutene reaction product results in its hydrolysisto form inorganic phosphorus acids in addition to the hydrolyzed organic product. Hereinbefore and hereinafter the term polybutene denotes, derivatives of isobutene as well as butene. The inorganic phosphorus acids are removed from the hydrolyzed product prior to reaction with alkene oxide via standard procedures such as those disclosed in U.S. 2,987,512 and U.S. 2,951,835 wherein removal is effected by contact withsynthetic hydrous alkaline earth metal silicates and synthetic hydrous alkali metal silicates, respectively. Inorganic phosphorus acids can also be removed by extraction with anhydrous methanol as disclosed in U.S. 3,135,729. Steam hydrolyzed inorganic phosphorus acid product is then contacted with ethylene oxide at a temperature between about 140 and 300 F. under pressure ranging from 0 to 50 p.s.i.g. utilizing a mole ratio of ethylene oxide to hydrolyzed hydrocarbon-P 8 reaction product of between about 1:1 and 4:1, preferably between about 1.121 and 15:1. Excess ethylene oxide is removed after completion of the reaction by blowing the reaction mixture at an elevated temperature, generally with inert gas such as nitrogen. The foregoing reactions are conducted in the presence of a hydrocarbon lubricating oil described in connection with the sulfurized normal calcium alkylphenolate. The lubracting oil normally Specific examples of the ethoxylated derivative of the reaction mixture. The introduction of the hydrocarbon lubricating oil normally takes place subsequent to steam hydrolysis. The ethoxylated derivative on an oil free basis normally has a sulfur content of between about 2 and 5 wt. percent and a phosphorus content of between about 4 and 6 wt. percent.

Specific examples of the ethoxylated deriavtive of the inorganic phosphorus acid free, steam hydrolyzed polybutene-P 8 reaction product are ethoxylated steam hydrolyzed polyisobutene (1100 M.W.)-P S reaction product, ethoxylated, steam hydrolyzed polybutene (1500 M.W.)-P S reaction product, ethoxylated, steam hydrolyzed polybutene (800 M.W.)-P S reaction product, ethoxylated, steam hydrolyzed polyisobutene (2000 M.W.)-P S reaction product where the ethylene oxide component and the reaction product component are present in a mole ratio of 1:1.

;In the method of producing the sulfurized calcium alkylphenolate compositions of the invention the reason why the bracketing of the sulfurization step with the first and second calcium alkoxyalkoxide additions as defined produces compositions of reduced corrosivity to copper and copper-lead bearings and resistance to oxidation as measured by viscosity increase is not truly understood. It is theorized, however, that when only one calcium alkoxyalkoxide addition is employed (and this must be done prior to sulfurization since sulfurization of alkylphenol does not readily occur), there remains at the end of the first stage reaction some unreacted calcium reagent when employing a stoichiometric or greater amount of calcium reagent. It is believed that hydrogen sulfide and other volatile acidic sulfur by-products evolve during the second stage sulfurization which could be removed by stripping, react with the leftover calcium reagent to form non-volatile calcium sulfur salts which remain in the product. The trapped acidic sulfur materials appear to significantly contribute to the corrosivity of the final product and its oxidative deterioration. It is further theorized that the reasons that the calcium reagent does not fully react with the alkylphenol in stoichiometric and excess stoichiometric amounts is that in the alkylated phenols there is always dialkylated phenols present. Dialkylated phenols are not easily neutralized. In contrast, in the three-stage process when less than stoichiometric amount of calcium reagent is employed the excess monoalkylated phenol ensures the tying up of all the calcium reagent so there is none to react with the acidic sulfur by-product formed during sulfurization, these by-products being removed as overhead in the second stage. The additional calcium reagent introduced in the third step reacts with the leftover monoalkylated phenol and any dialkylated phenol which may be present.

In support of the above theory, it appears for a given calcium content in the final product, the final product which employs the bracketing calcium alkoxyalkoxide treatment rather than reacting all the calcium alkoxyalkoxide prior to sulfurization produces a product having a greater total base number per unit calcium, that is, a greater alkaline calcium activity. Greater alkalinity produces a less corrosive product of greater detergent dispersancy and less undesired viscosity increase under engine conditions.

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 product of the invention. To a 2-liter flask fitted with a Dean-Stark trap and an inert gas inlet there was charged 280 grams (1 mole) of 4-dodecyclphenol and 350 grams of a naphthenic lubricating oil of an SUS viscosity of about at 100 F. and the reactor atmosphere was purged with nitrogen. The resultant mixture was heated with stirring to a temperatureof about 350 F. under a blanket of nitrogen and grams (0.25 mole calcium) of a 34 wt. percent solution of calcium methoxyethoxide in methoxyethanol were added and the reaction mixture was stripped over a 20 minute period with nitrogen blowing at a rate of 500 mls./min./liter while heating the mixture to 410 F. Powdered sulfur in an amount of 40 grams (1.25 moles) was added with continued stirring and the mixture was kept at 410 F. for a period of 3 hours while sequentially blowing 1 hour with nitrogen, 1 hour with carbon dioxide and then 1 hour with nitrogen at a gas rate of 500 mls./min./1iter. At the end of the 3 hour period an additional portion in an amount of 140 grams of calcium methoxyethoxide solution was added dropwise and the solvent was removed as overhead while maintaining the reaction mixture at 410 F. The product yield was 658 grams (95 wt. percent of theory). An analysis of the product determined it to be a lube oil solution of sulfurized calcium dodecylphenolate, the solution giving the following analysis: wt. percent Ca: 2.62; wt. percent S: 2.55; TBN (total base number): 81.

7 EXAMPLE 11 This example illustrates the comparative prior procedure for the formulation of sulfurized calcium alkylphenolate.

To a 2-liter flask equipped with a Dean-Stark trap and inert gas inlet and stirrer there was charged 280 grams (1 mole) of 4-dodecylphenol and 350 grams of naphthenic lubricating oil having an SUS viscosity of about 100 at 100 F. The mixture was stirred under a blanket of nitrogen and heated to about 330 F. Two hundred and eighty grams (0.5 mole calcium) of a 34 wt. percent solution of calcium Z-methoxyethoxide in methoxyethanol was added dropwise over a half-hour period and then ethoxyethanol solvent was removed overhead. The temperature was gradually increased to 410 F. and when methoxymethanol ceased to evolve overhead 40 grams (1.25 moles) of powdered sulfur were added. The mixture was kept at 410 F. for 5 hours with stirring. The first 3 hours were maintained under a nitrogen blanket followed by 1 hour of CO blowing and 1 hour of nitrogen blowing. The blowing rates were 500 mls./min./liter solution. The product was filtered hot through diatomaceous earth and a lube oil solution was recovered in a. yield of 626 grams (95 wt. percent of theory). Analysis determined the product to be a lube oil solution of sulfurized calcium dodecylphenolate having wt. percent calcium: 2.89; wt. percent sulfur: 2.75; TBN: 83.

EXAMPLE HI Utilizing the general procedure outlined in Examples I and II, the following additional lube oil compositions were prepared: The Example I general procedure was employed in all runs save Runs H and 1. Example II procedure was employed in Runs H and I. The ingredients, quantities, percent of neutralization (percent of stoichiometric of the calcium reagent employed in the first stage) and product analysis are set forth in the following Tables I and II:

TABLE I.SYNTHESIS Grams Grams 1st Ca. 2nd Ca. C11 alkylreag. Percent reag.

phenol add. 1st neut. 5 add. Oil

Run:

280 70 25 40 210 350 B 280 140 50 40 130 325 C- 295 (1 m.) 162 55 48 133 340 D- 295 (1 m.) 177 60 56 118 340 TAB LE II.ANALYSIS Wt. percent Wt. percent Percent Ca S TBN 1st meat.

EXAMPLE IV The concentrates prepared in Example III were utilized to formulate finished lubricant compositions and the finished compositions were subjected to a well known railway diesel lube oil oxidation test. In the test procedure a copper-lead surface bearing is inserted in test oil. The oil is kept at 285 F. and the air (5 liters/hour) is bubbled through for 72 hours. At the end of the test the bearing weight loss (BWL) and viscosity increase of the oil are measured. Normal limits for the test are 50 mg. BWL

max., and 15% viscosity increase max. The finished compositions were of the follownig average make-up:

Components Weight; percent Mineral lube oil (-1, 000 SUS at 100 F.) 00. 3 89. 8 88. 8 Sulfurized normal Ca alkylphenol concentrate e 6. 5 7. 0 8. 0 Ethoxylated derivatives concentrate b 3. 2 3. 2 3. 2

The test data and results are reported below in Table III.

TABLE III TABLE III.EVALUATION Oxidation test Wt. percent Percent cone. in Percent ca. BWL. Percent 1st neut. comp. in comp. mg. vise. inc.

Run:

A- 25 7.0 0.20 31 12.0 B 50 6.5 0.22 12 6.8 0---- 55 6.5 0.20 2.9 6.4 D. 60 6.5 0. 29 2.9 E 75 6.5 0.23 9.3 6.5 0. 24 18 8. 9 G. 6.5 0. 23 22 8.6 H-

We claim: 1. A lubricating oil composition comprising a ma or amount of a hydrocarbon oil of lubricating viscosity conthe formula:

where R is alkyl of from 5 to 50 carbons with a first addition of calcium alkoxyalkoxide of the formula:

CatO-A-OR' 2 where A is alkanediyl of from 1 to 6 carbons and R is alkyl from 1 to 25 carbons at a first temperature between about 200 and 425 F. utilizing a mole ratio of said calcium alkoxyalkoxide to said alkylphenol of between about 0.255 :1 and 0.45:1, second contacting the resultant mixture with sulfur in the presence of a hydrocarbon lubricating oil at a second temperature between about 350 and 425 F. utilizing a mole ratio of sulfur to initial alkylphenol of between about 0.5 :1 and 8:1 while simultaneously blowing the reaction mixture with an inert gas at a gas rate of between about 0.1 and 10 s.c.f.h./ gallon, continuing said blowing until sulfide content of said reaction mixture is less than 3 p.p.m., and subsequently third contacting the blown mixture with a second addition of calcium alkoxyalkoxide at said second temperature in a mole.

ratio of calcium alkoxyalkoxide to initial alkylphenol of between about 0.15:1 and 0.37 5:1 in sufficient amount so that the total calcium alkoxyalkoxide employed in the first and third contacting will total a mole ratio of calcium alkoxyalkoxide to initial alkylphenol of between about 0.5:1 and 0.621.

2. A lubricating oil composition in accordance with claim 1 wherein the reaction mixture during said first and third contactings is blown with inert gas at a gas rate of between about 0.1 and 10 s.c.f.h./ gallon.

3. A lubricating oil composition in accordance with claim 1 wherein said inert gas is nitrogen.

4. A lubricating oil composition in accordance with claim 1 wherein said alkylphenol is dodecylphenol, said calcium alkoxyalkoxide is calcium methoxyethoxide in a 34 wt. percent solution of methoxyethanol and in said second contacting the reaction mixture is blown sequentially with nitrogen, carbon dioxide and then nitrogen.

5. A lubricating oil composition in accordance with claim 1 containing between about 0.1 and 7.5 wt. percent of said sulfurized normal calcium alkylphenolate.

6. A lubricating oil composition in accordance with claim 1 containing between about 0.1 and 7.5 wt. percent of said sulfurized normal alkylphenolate and between about 0.3 and 6 wt. percent of an ethoxylated inorganic phosphorus acid free, steam hydrolyzed, polybutene (800- 2500 M.W.)-P S reaction product, said ethylene oxide 10 mioety being present in respect to said steam hydrolyzed po1ybutene-P S reaction product in a mole ratio of about 1:1 and the polybutene-P S components being present in a mole ratio to one another of between about 1:1.

References Cited UNITED STATES PATENTS 3,474,035 10/1969 Dadura 252-427 3,528,917 9/1970 Dadura 252-427 3,549,534 12/1970 Holstedt 25242.7

HELEN M. S. SNEED, Primary Examiner mg UNITED STATES PATENT OFFICE Page CERTIFICATE OF CORRECTION Patent No. 3,7bl, ll l Dated September 25 1973 Invent r) HAAKEN HAUGEN and HARRY CHAFETZ It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 5, line 59, change "deriavtive" to --derivative--.

Col. 8, line 50, change "0.255zl" to --O.225:1--.

Signed and sealed this 25th day of June 197M.

(SEAL) Attest:

EDWARD M.FLETCHER,JR; C. MARSHALL DANN Attesting Officer Commissioner of Patents 22 3 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,7 Dated September 25, 1973 Inventofle) HAAKON HAUGEN and HARRY CHAFETZ It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

E301. 3, lines 7- change "iner gas blowing until no "1 detectable H 8 odor is found tiles" to --inert gas functions to facilitate removal of reaction volatiles---.

C01. 4, line change "0. O5" to --O. O1-.-.

Col. l, line 66, change "actually" to -actuality-.

Col. 5, line 51, change "lubracting" to --lubricating--.

Col. 5, line 51, after "normally" add --constitutes between about 20 and 80 wt. of the reaction mixture. The introduction of the hydrocarbon lubricating oil normally takes place subsequent to steam hydrolysis--.

Col. 5, lines 52-56, cancel "Specific examples of the I ethoxylated deriya'tive of the reaction mixture. The introduction of the hydrocarbon lubricating oil normally takes place subsequent to steam hydrolysis".