Abstract:
A lubricant composition is provided as follows:
       At least 90% of a base grease;   (a) a thiadiazole poly(ether)glycol complex in an amount which provides about 1500 to 3500 ppm sulfur;   (b) molybdenum dihydrocarbyldithiophosphate in amount which provides about 77 to 450 ppm molybdenum; and   (c) zinc dihydrocarbyldithiophosphate in an amount which provides about 600 to 1000 ppm zinc. An additive composition for grease, consisting of components (a), (b) and (c), is also provided.

Description:
FIELD OF INVENTION 
     The present invention is directed to an additive composition for extreme pressure (“EP”) grease compositions having exceptional antiwear and corrosion properties. More specifically, the invention relates to an additive composition comprising (A) thiadiazole poly(ether)glycol complex (B) molybdenum dihydrocarbyldithiophosphate and (C) zinc dihydrocarbyldithiophosphate. 
     BACKGROUND 
     EP greases lubricate under highly loaded conditions and require highly effective EP additives to prevent scoring and welding. Thiadiazoles are compounds that are effective EP additives. U.S. Pat. No. 6,365,557 discloses thiadiazole/poly(ether)glycol complexes. Although these complexes are excellent extreme pressure additives for greases, their high surface affinity to metals surfaces produces coatings that generate undesirable discoloration of copper and other non-ferrous metals and block the ability of antiwear additives to reduce wear. The invention herein teaches specific lubricant additive composition in which these thiadiazole poly(ether)glycol complexes do not have negative impact on wear and corrosion while maintaining the exceptional extreme pressure properties. 
     U.S. Pat. No. 6,541,427 (Dresel et al.) discloses a grease formulation having additive system that contains 2% molybdenum compound (dihydrocarbyldithiocarbamate, MoDTC or dihydrocarbyldithiophosphate MoDTP), about 2% thiadiazole derivative and requires an assortment of other additives. 
     SUMMARY OF THE INVENTION 
     The invention relates to a lubricant composition comprising the following components, all in weight %:
         (a) Major amount (i.e. &gt;90%) of base grease, such as lithium, lithium complex, aluminum complex, calcium complex organo-clay and polyurea.   (b) Thiadiazole poly(ether)glycol complex providing 1500 to 3500 ppm sulfur (S), preferably 2000 to 2800 ppm S;   (c) Molybdenum dihydrocarbyldithiophosphate providing 77 to 450 ppm molybdenum (Mo), preferably 192-220 ppm Mo;   (d) Zinc dihydrocarbyldithiophosphate providing 600 to 1000 ppm zinc (Zn), preferably 700 to 900 ppm Zn.       

     The invention also discloses an additive composition for use in grease. The additive composition is comprised of the following compounds:
         (a) Thiadiazole poly(ether)glycol complex;   (b) Molybdenum dihydrocarbyldithiophosphate;   (c) Zinc dihydrocarbyldithiophosphate.
 
at the S:Mo:Zn weight ratio of about 150-350:7.7-45:60-100. In this ratio, the S refers to sulfur provided by the thiadiazole/poly(ether)glycol complex.
       

    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Thiadiazole/poly(ether)glycol complexes of this invention are described in U.S. Pat. No. 6,365,557, incorporated herein by reference. Preferred embodiments comprise a complex of: 
     (a) one or more thiadiazole compound as follows:
         (i) dimers of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) having the formula:       

                                
wherein n is 1 and/or 2; and/or
         (ii) 2-mercapto-1,3,4-thiadiazole (MTD) having formula:       

                                
and (b) poly(ether)glycol having formula:
 
                                
wherein R 1  is hydrogen, a branched or straight chain C 1  to C 20  alkyl radical, a phenyl radical, a C 1  to C 8  branched straight chain acyl radical, and combination thereof, and m is 1 to 300. Preferred poly(ether)glycols are butoxytriglycol, polyethylene glycol or a combination thereof, with the latter combination being most preferred.
 
     As set out above, the 
     (a) thiadiazole may be one or more of the mono sulfide dimer of DMTD (Formula I, n=1), disulfide dimer of DMTD (Formula I, n=2) and MTD (Formula II); and such is to be complexed with 
     (b) poly(ether)glycol (Formula III). 
     The complex may comprise, by weight, from about 10% to 60% thiadiazole compound(s) and about 40% to 90% poly(ether)glycol compound(s); preferably about 25% to 50% thiadiazole compound(s) and about 50% to 75% poly(ether)glycol compound(s); and most preferably about 30% to 40% thiadiazole and about 60% to 70% poly(ether)glycol. 
     A most preferred embodiment for the complex is available as Vanlube® 972M additive from R.T. Vanderbilt Company, Inc. of Norwalk, Conn. Vanlube 972M comprises approximately, by weight: (a) 15% of mono sulfide dimer of DMTD, 10% disulfide dimer of DMTD, 10% of MTD; and (b) 49% butoxytriglycol and 16% polyethylene glycol; and has an average molecular weight of 300 grams per mole. 
     Molybdenum and zinc dihydrocarbyldithiophosphate compounds are usually prepared by reacting P 2 S 5  with alcohols to form dihydrocarbyldithiophosphoric acid compounds, which are then neutralized with suitable molybdenum or zinc compounds: 
                                
wherein R 2  and R 3  are independent hydrocarbyl groups containing 1 to 18 preferably 2 to 12 carbon atoms including alkyl, alkenyl, aryl, arylalkyl, alkylaryl and cycloaliphatic groups. Examples of hydrocarbyl groups are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, iso-octyl, 2-ethylhexyl, and butylphenyl. In the case of molybdenum dihydrocarbyldithiophosphate, o is 2 and 4; x is 1 to 2; y is 1 to 4; and z is 1 to 4.
 
     Test Methods 
     Test methods used in this invention to evaluate extreme pressure, corrosion resistance, and wear properties of grease compositions were the following:
         1. Timken EP Test   2. Copper Strip Test   3. 4-Ball Wear Test       

     The Timken test is a well-known standardized test, and described in ASTM D 2509. The Timken test measures the loads at which abrasive wear, i.e. scoring, occur between a rotating cup and stationary block; thus, the higher the Timken OK load, the better the EP properties of the grease. An informal EP ranking based Timken OK load performance is provided below; wherein anything in the range 60-80 (excellent or exceptional) is considered acceptable to industry standards: 
                                 Timken OK Load, (lb.)   EP Performance Ranking                   80   Exceptional       60-70   Excellent       50   Good       40   Marginal                    
Copper strip test method, ASTM D 4048, was used to evaluate copper corrosion characteristics of grease compositions. In this test method, the polished copper strip is totally immersed in a sample of grease and heated in an oven at 100° C. for 24 hours. At the end of this period, the strip is removed, washed, and compared with the ASTM Copper Strip Corrosion Standards. A copper strip is assigned a rating of  1   a  to  4   b . A rating of  1   a  represents a strip with the least amount of corrosion and  4   c  represents a strip with the maximum amount of corrosion. Commercial greases are non-corrosive and produce ratings no higher than  1   b.  
 
     Four-Ball Wear Tests are conducted according to standard procedure described in ASTM D4172. In this test method, one ball is rotated on three evenly spaced static balls while the four balls are completely submerged under the test oil. The tests for this invention were conducted at a rotation speed of 1200 rpm under a load of 40 kg for one hour at 75° C. The scar diameter of three static balls is measured and the result is the average of the three. An acceptable result for this test is an average wear scar that is less 0.5 mm in diameter. 
     Example 1 
     Lithium grease containing thiadiazole poly(ether)glycol complex (Vanlube® 972M additive available from R.T. Vanderbilt Company, Inc. of Norwalk, Conn.), Vanlube 972M in combination molybdenum dialkyldithiophosphate (Molyvan® L additive available from R.T. Vanderbilt Company, Inc.), Vanlube 972M in combination zinc dialkyldithiophosphate (Lubrizol® 1395, available from Lubrizol Corp.) diluted with 10-20% oil and Vanlube 972M in combination with Molyvan L and Lubrizol 1395, were evaluated for wear, EP and corrosion properties. The data as summarized Table 1 shows that only the greases treated with all three components and particular concentrations carried excellent to exceptional Timken OK loads with acceptable wear scars and copper corrosion ratings. In addition, data for formulation 10, 11, 12 and 13 indicate that other molybdenum compounds such molybdenum dialkyldithiocarbamates (Molyvan® 822) and organo-molybdates (Molyvan® 855) are not effective alternatives to MoDTP. 
     
       
         
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
                 9 
                 10 
                 11 
                 12 
                 13 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Vanlube 972M 1   
                 2.0 
                 1.0 
                 2.0 
                 2.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
                 1.0 
               
               
                 Lubrizol 1395 2   
                 — 
                 — 
                 1.0 
                 — 
                 1.0 
                 — 
                 — 
                 0.50 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
               
               
                 Molyvan L 3   
                 — 
                 — 
                 — 
                 1.0 
                 — 
                 1.0 
                 0.5 
                 0.25 
                 0.25 
                 — 
                 — 
                 — 
                 — 
               
               
                 Molyvan 822 4   
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.25 
                 0.50 
                 — 
                 — 
               
               
                 Molyvan 855 5   
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.25 
                 0.50 
               
               
                 S Content, ppm 
                 4800 
                 2400 
                 4800 
                 4800 
                 2400 
                 2400 
                 2400 
                 2400 
                 2400 
                 2400 
                 2400 
                 2400 
                 2400 
               
               
                 Mo Content, ppm 
                 0 
                 0 
                 0 
                 825 
                 0 
                 825 
                 412 
                 206 
                 206 
                 123 
                 246 
                 198 
                 396 
               
               
                 Zn Content, ppm 
                 0 
                 0 
                 1060 
                   
                 1060 
                 0 
                 0 
                 530 
                 795 
                 795 
                 795 
                 795 
                 795 
               
               
                 4-Ball Wear, mm 
                 0.64 
                 0.58 
                 0.61 
                 0.52 
                 0.53 
                 0.46 
                 0.44 
                 0.47 
                 0.46 
                 0.52 
                 0.51 
                 0.48 
                 0.53 
               
               
                 Timken OK Load, lb. 
                 80 
                 Fail 40 
                 — 
                 — 
                 — 
                 — 
                 70 
                 60 
                 80 
                 Fail 
                 Fail 
                 Fail 
                 — 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 40 
                 40 
                 40 
               
               
                 Copper corrosion 
                 2e 
                 2e 
                 4a 
                 2e 
                 3a 
                 4b 
                 2e 
                 3a 
                 1b 
                 1b 
                 1b 
                 1b 
                 1b 
               
               
                   
               
               
                   1 Sulfur content of Vanlube 972M is 24% (by weight). 
               
               
                   3 Zinc content of Lubrizol 1395 is 10.6 percent %. 
               
               
                   3 Molybdenum content of Molyvan L is 8.3%. 
               
               
                   4 Molybdenum content of Molyvan 822 is 4.9%. 
               
               
                   5 Molybdenum content of Molyvan 855 is 7.9%. 
               
             
          
         
       
     
     Example 2 
     Comparative Examples 
     As comparative examples, ZDDP component of the invention was substituted with other phosphorus and zinc based antiwear (AW) additives while keeping the other components of the invention constant. As summarized in Table 2, none of alternatives provided satisfactory antiwear performance with exception of zinc naphthenate. However, EP performance of zinc naphthenate containing composition was unsatisfactory. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 (Comparative Examples) 
               
             
          
           
               
                   
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
               
               
                   
                   
               
             
          
           
               
                 Vanlube 972M 
                 1.00 
                 1.00 
                 1.00 
                 1.00 
                 1.00 
                 1.00 
               
               
                 Molyvan L 
                 0.25 
                 0.25 
                 0.25 
                 0.25 
                 0.25 
                 0.25 
               
               
                 Vanlube 7611M 
                 0.75 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 (ashless dialkyldithiophosphate AW additive) 
               
               
                 Vanlube 9123 
                 — 
                 0.75 
                 — 
                 — 
                 — 
                 — 
               
               
                 (amine phosphate AW additive) 
               
               
                 Vanlube 727 
                 — 
                 — 
                 0.75 
                 — 
                 — 
                 — 
               
               
                 (ashless dialkyldithiophosphate AW additive) 
               
               
                 Vanlube 672 
                 — 
                 — 
                 — 
                 0.75 
                 — 
                 — 
               
               
                 (amine phosphate AW additive) 
               
               
                 Vanlube AZ 
                 — 
                 — 
                 — 
                 — 
                 1.30 
                 — 
               
               
                 (50% zinc dialkyldithiocarbamate) 
               
               
                 Zinc naphthenate 
                   
                   
                   
                   
                   
                 0.75 
               
               
                 4-Ball Wear, mm 
                 0.58 
                 0.53 
                 0.57 
                 0.56 
                 0.51 
                 0.47 
               
               
                 Timken OK Load, lb 
                 — 
                 — 
                 — 
                 — 
                 — 
                 Fail 
               
               
                   
                   
                   
                   
                   
                   
                 40 
               
               
                 Copper corrosion 
                 — 
                 — 
                 — 
                 — 
                 3a 
                 1b 
               
               
                   
               
             
          
         
       
     
     Example 3 
     Comparative Examples 
     For comparison, thiadiazole poly(ether)glycol complex component of the invention was exchanged with other thiadiazole derivatives. As summarized in Table 3, none of alternatives provided satisfactory EP performance: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 (Comparative Examples) 
               
             
          
           
               
                   
                 20 
                 21 
               
               
                   
                   
               
             
          
           
               
                 Lubrizol 1395 (ZDDP) 
                 0.75 
                 0.75 
               
               
                 Molyvan L 
                 0.25 
                 0.25 
               
               
                 Vanlube 829 
                 0.37 
                 — 
               
               
                 (Thiadiazole disulfide dimer used at equivalent 
               
               
                 sulfur content as 1% Vanlube 972M) 
               
               
                 Cuvan ® 826 
                 — 
                 0.77 
               
               
                 (Thiadiazole derivative used at equivalent sulfur 
               
               
                 content as 1% Vanlube 972M) 
               
               
                 4-Ball Wear, mm 
                 0.43 
                 0.44 
               
               
                 Timken OK Load, lb 
                 30    
                 20    
               
               
                 Copper corrosion 
                 1b   
                 1b