Abstract:
A grease compound of a base oil, a thickener, and minor synergistic amounts of the extreme pressure agent combination of zinc dialkyldithiophosphate, the reaction product of butyl acid phosphate and dodecyl aniline, and Bis(β-chlorophenethyl) disulfide.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention pertains to the field of lubricants, especially greases. 
     2. Description of the Prior Art 
     It is desirable in the selection of greases to consider the environment that the greases will have to operate under and in many cases, to select a grease which has properties which will allow it to perform adequately where two surfaces come together with considerable force. This force makes it very difficult to keep a lubricant in place and prevent the two surfaces from actually touching each other. A lubricant between these surfaces must possess a property known as extreme pressure (EP) tolerance. This property allows a lubricant to continue to lubricate the two surfaces even though the bulk of the grease is forced out from between the surfaces. The art has many references to additives which impart extreme pressure properties to greases. It was surprising, however, to discover that a particular combination of additives imparted synergistic extreme pressure properties to greases. That is, the extreme pressure properties of the resulting grease having the combination of additives as disclosed by applicant, are superior to greases containing only one or two components of the proposed three component additive combination. By using the additive combination disclosed hereinafter, a grease may be obtained which has unexpectedly superior extreme pressure properties. 
     SUMMARY OF THE INVENTION 
     The invention is a lubricant, especially a grease, comprising a major amount of a lubricating oil, a thickener and a three component additive combination to impart synergistic extreme pressure properties. This three component additive combination consists of zinc dialkyldithiophosphate, Bis(β -chlorophenethyl) disulfide and the reaction produce of butyl acid phosphate and dodecyl aniline. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The lubricating oils forming the major component of the grease compositions claimed hereinafter may be any lubricating oil having Saybolt Universal viscosities in the range of from about 75 seconds at 100°F. (75SUS/100°F.) to about 225 seconds at 210° F., which may either naphthenic or paraffinic in type, or blends comprising both naphthenic and paraffinic oils. The preferred lubricating oils are those having Saybolt Universal viscosities in the range of from about 300 seconds at 100° F. to about 100 seconds at 210° F., which may be blends of lighter and heavier ols in a lubricating oil viscosity range. Synthetic lubricating oils which may be preferred in preparing greases having particular properties required for special types of lubricating services, include oils prepared by cracking and polymerizing products of the Fischer-Tropsch process and the like as well as other synthetic oleaginous compounds such as polyethers, polyesters, silicon oils, etc. having viscosities within the lubricating oil viscosity range. Suitable polyethers include particularly polyalkylene glycols such as polyethylene glycol. Suitable polyesters include the aliphatic dicarboxylic acid diesters, such as di- 2-ethyl-hexyl secabacate, di(secondary amyl) sebacate, di-2-ethyl-hexyl azelate, di-iso-octyl adipate, etc. The sulfur analogs of the polyalkylene esters and polyesters are also suitable. 
     Silicon polymer oils may also be employed, preferably having viscosities in the range from about 70 to 900 seconds Saybolt Universal at 100° F. Suitable compounds of this type include dimethyl silicon polymer, diethyl silicon polymer, methyl cyclohexyl silicon polymer, diphenol silicon polymer, methyl ethyl silicon polymer, methyltolyl silicon polymer, etc. The lubricating oils normally comprise from about 70 to 98 percent of the grease composition. 
     Generally, two types of thickeners for the oils are used to form the greases: soaps and/or clays. 
     By the term soap base thickening agent as used herein, it is meant metal soaps of fatty acids which are capable of providing a stable gell structure to lubricating base oils. The term soap is intended to include conventional metal soaps, complex soaps, mixed base soap greases, and the like, and to include, for example, the following particular types of soap thickeners: 
     Metal Base 
     Aluminum base 
     Barium base 
     Calcium base 
     Lithium base 
     Sodium base 
     Lead base 
     Strontium base 
     Mixed Bases 
     Sodium-calcium base 
     Sodium-barium base 
     Calcium-aluminum base 
     Magnesium-aluminum base 
     Lithium-aluminum base 
     Lithium-calcium base 
     Sodium-Aluminum Base Metal Complex 
     Hydrated calcium soap 
     Hydrated aluminum soap 
     Hydrated barium soap 
     Hydrated lithium soap 
     Hydrated sodium soap 
     Hydrated strontium soap 
     Complex aluminum soap 
     Complex barium soap 
     Aluminum-barium complex 
     Aluminum-sodium complex 
     Complex calcium soap 
     Calcium soap-calcium acetate complex 
     Calcium soap-calcium chloride complex 
     Calcium soap-strontium hydrate complex 
     Calcium-barium soap complex 
     Complex lithium soap 
     Lithium soap-lithium acetate 
     Lithium soap-lithium acelate complex 
     Magnesium soap complex 
     Lead soap complex 
     Sodium soap-sodium acetate complex 
     Sodium soap-sodium acrylate complex 
     Sodium-barium complex 
     Strontium-calcium acetate complex 
     Though the lubricating base oil component of the invention can be either a natural or synthetic oil, as a practical matter, the base oil will usually be a natural oil, e.g., a petroleum-derived mineral oil. Many synthetic oils such as silicone oils and various esters can be thickened effectively with soap thickeners; however, the thermal stability of soaps is usually considerably lower than that of the synthetic oils. Therefore, there is usually no point in using expensive synthetic oils with soap greases. Exceptions to this, however, are some of the complex greases which possess considerably higher thermal stability than the conventional soap-base greases. 
     The clays which are useful as thickeners for the preparation of greases are oleophilic clay products exhibiting a substantial base exchange capacity. The clays particularly contemplated herein include especially the montmorillonites, such as socium, potassium, lithium, and the other bentonites, particularly of the Wyoming bentonite type. Still more preferred are the magnesium bentonites, sometimes referred to as &#34;Hectorites.&#34; These clays are characterized by unbalanced crystal structure and are believed to have negative charges which are normally neutralized by inorganic cations. An especially preferred bentonite is that made by complexing finely particulated montmorillonite in aqueous media with dimethyldioctadecyl ammonium chloride using the techniques described in U.S. Pat. Nos. 2,531,427 and 2,531,440. This product can be purchased under the coined name &#34;Bentone 34&#34; from the Baroid Sales Division of National Lead. 
     The term &#34;oleophilic clay product&#34; is meant to include such clays when they have absorbed thereon or reacted therewith sufficient organic ammonia base to form an oleophilic product. The so-called &#34;onium-clays&#34; comprise reaction products of oleophilic ammonium bases (or their salts) and clays. 
     The clays are more preferably modified by absorption of one or more oleophilic cationic surface-active agents such as those described in U.S. Pat. Nos. 2,831,809 and 2,874,152. The clays are preferably present in an amount sufficient to cause grease formation of the lubricating oil to occur. This will usually occur in the range of 2.5-10% by weight of the high base exchange clay (based on the inorganic clay portion of the oleophilic clay product) depending somewhat upon the precise clay employed, the chemical constitution of the major lubricating oil components and the proportions of other components present in the grease formulation. 
     The thickeners used in my invention normally comprise from about 3  to 10% of the grease. 
     The three component additive combination of this invention comprises 
     1. zinc dialkyldithiophosphate in an amount ranging from about 1 to 3 weight percent of the total lubricant mixture and preferably in an amount ranging from about 1.5 to 2.5 weight percent of the total lubricant mixture. 
     2. Bis(β-chlorophenethyl) disulfide in an amount ranging from about 1 to 3 weight percent of the total lubricant mixture and preferably in an amount ranging from about 1.5 to 2.5 weight percent of the total lubricant 
     3. The reaction product of butyl acid phosphate and dodecyl aniline. The composition of this reaction product is a mixture of monobutyl and dibutyl acid phosphates and dodecyl aniline in the form of a salt. Specificially, the reaction product is a salt of dodecyl aniline comprising about 70 weight percent, monobutyl acid phosphate comprising about 13 weight percent and dibutyl acid phosphate comprising about 17 weight percent. The additive also includes trace amount of paraffin oils, water and butyl alcohol. This additive should be present in the lubricant in an amount ranging from about 0.2 to 1.0 weight percent of the total lubricant mixture and preferably in an amount ranging from about 0.4 to 0.6 weight percent of the total lubricant mixture. 
     In addition to the additive combination of this invention, other additives of the types ordinarily employed in lubricating compositions may be employed in these greases such as oxidation inhibitors, corrosion inhibitors, and tackiness agents. 
     PREPARATION OF A TYPICAL GREASE OF THE INVENTION 
     A suggested procedure for making a grease of my invention includes the following steps: 
     1. Lithium hydroxide and a fat are saponified in the presence of a portion of the base oil with stirring. 
     2. The mixture is heated with stirring above the melting point of the soap formed in (1), above and then quenched with additional base oil. 
     3. Any additional base oil is then added as the mixture is stirred and the additives are then added. 
     4. The grease mixture may then be passed through a colloid mill to further disperse the soap. 
     The procedure above is only suggested. Any method for making grease accepted in the art may be used. The invention is not restricted to my particular method of making grease. 
     EXPERIMENTAL 
     Greases were made as described above from an uninhibited lithium soap base and the additive combinations shown below. As may be seen, the three component system gave test results superior to any grease made with the same amount of any two of the additives. 
     
         ______________________________________            GREASEINGREDIENTS, WT. %            A       B       C     D______________________________________Base oil*        87.9    87.9    87.9  87.9Lithium Soap     7.6     7.6     7.6   7.6Reaction Product of butyl acid phosphate and dodecylaniline            0.5     0.5     --    0.5Bis(β-chlorophenethyl) disulfide       4.0     2.0     2.0   --Zinc Dialkyldithio- phosphate       --      2.0     2.5   4.0Tests:Load Wear Index, Kg.            70.6    73.2    61.7  50.1Weld Point, Kg.  316     398     316   251Timken, OK, lb.  35      45      35______________________________________ *Parraffinic oil of about 1000 SUS/100° F. 
    
     The data below indicate the effect of the additive package in grease B above at different concentrations: 
     
         ______________________________________             GREASEINGREDIENTS, WT. %             B        E        F______________________________________Base oil*         87.9     87.9     87.9Lithium Soap      7.6      7.6      7.6Reaction Product of butyl acid phosphate and dodecylaniline             0.5      0.5      0.5Bis(β-chlorophenethyl) disulfide        2.0      3.0      1.0Zinc Dialkyldithio phosphate             2.0      2.0      3.0Tests:Load Wear Index, Kg.             73.2     63.5     47.6Weld Point, Kg.   398      251      316Timken, Kg        45       30       40______________________________________