iiililiili^ @ EuroPean Patent Office ^-S Office europeen des brevets (fi) Publication number : 0 586 258 A2 12 EUROPEAN PATENT APPLICATION @ Application number: 93306992.4 @ Int. CI.5: C10M 159/20, C10M 169/00, C10M 173/00, C10L 1/24 (22) Date of filing : 03.09.93 (30) Priority : 04.09.92 US 940594 (72) Inventor : Cahoon, John Melvin 8743 Marjory Drive Mentor, Ohio 44060 (US) Date of of (43) publication application : Inventor : Karn, Jack Lee 09.03.94 Bulletin 94/10 622 Dade Lane Richmond Heighs, Ohio 44143 (US) @ Designated Contracting States : Inventor : Huang, Nai Zhong AT BE CH DE DK ES FR GB GR IE IT LI LU MC 5879 Cantwell Drive NL PT SE Mayfield Heights, Ohio 44124 (US) Inventor : Roski, James Peter 19830 Lakeshore Boulevard (n) Applicant : The Lubrizol Corporation Euclid, Ohio 44119 (US) 29400 Lakeland Boulevard Wickliffe, Ohio 44092 (US) (74) Representative : Mallalieu, Catherine Louise et al D. Young & Co., 21 New Fetter Lane London EC4A 1DA (GB) @) Sulfurized overbased compositions. (57) This invention relates to a composition comprising at least one sulfurized overbased product made by contacting (A) at least one overbased product or (A') at least one boron-containing overbased product with (B) sulfur and/or at least one source of sulfur ; said overbased product (A) or boron-containing overbased product (A') being made using at least one acidic material, with the proviso that when said acidic material is other than S02 or a source of S02 said overbased product (A) or boron-containing overbased product (A') is contacted with an effective amount of S02 or a source of S02 to displace at least part of said acidic material. In one embodiment the sulfurized overbased product is an overbased thiosulfate or a boron-containing overbased thiosulfate. In one embodiment, the sulfurized overbased product is made using the overbased product (A) and the composition further comprises at least one non-sulfurized boron-containing overbased product. The sulfurized overbased products are thermally stable and are useful as extreme pressure (EP) and/or anti-wear agents or antioxidants for use in lubricants, functional fluids and normally liquid fuels. The functional fluids can be oil-based, water-oil emulsions or water-based. The sulfurized overbased products are particularly suitable for use as EP and/or anti-wear agents for use in gear lubricants and cutting fluids. In one embodiment lubricating compositions are provided that pass both the L-37 High Torque Test and the L-42 High Speed Shock Test without the necessity of employing phosphorus and sulfurized olefin anti-wear systems in their CM formulation. < 00 If) CM CO 00 If) LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 586 258 A2 Technical Field This invention relates to sulfurized overbased products which are useful as extreme pressure (EP) and/or anti-wear agents or antioxidants for use in lubricants, functional fluids and normally liquid fuels. The functional 5 fluids can be oil-based, water-oil emulsions or water-based. The sulfurized overbased products are thermally stable and are particularly suitable for use as EP and/or anti-wear additives for gear lubricants and cutting flu- ids. Background of the Invention 10 In the automotive and truck markets there is a continuing demand for smaller and lighter vehicles which in turn has resulted in a demand for smaller and lighter engines and drive train components (e.g., transmissions, axles, etc.). Because they are lighter and smaller these engines and drive train components must operate at higher speeds which, among other things, has led to a demand for lubricants having improved EP/anti-wear 15 characteristics as well as high temperature stability characteristics . EP/anti-wear agents heretofore employed in the art are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulf ides such as benzyl disulfide, bis(chlorobenzyl)disulf ide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sul- furized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with 20 turpentine or methyl oleate, phosphorus esters including principally dihydrocarbon and tri hydrocarbon phos- phites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipen- tylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarba- 25 mate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphor- odithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulf ide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol. The ash-producing detergents/dispersants heretofore used in the art include the oil-soluble neutral and 30 overbased salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, and certain organic phos- phorus acids. The term "overbased" salt is used herein to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. It is known to make overbased salts by contacting a reaction mixture comprising at least one organic ma- terial to be overbased, (e.g., sulfonic acid, carboxylic acid, phenol, certain classes of organic phosphorus 35 acids), a reaction medium consisting essentially of at least one inert, organic solvent/diluent for said organic material to be overbased (e.g., mineral oil), a stoichiometric excess of at least one metal base, (e.g., sodium hydroxide, calcium hydroxide, magnesium oxide), at least one promoter, (e.g., methanol, phenol) with at least one acidic material, (e.g., C02, S02) at an elevated temperature (e.g., 60-300°C). Methods for preparing these overbased salts as well as an extremely diverse group of overbased salts are well known in the art and are 40 disclosed, for example, in the following U.S. patents: 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234; 2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874; 2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951; 2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823; 3,223,630; 45 3,232,883; 3,242,079; 3,242,080; 3,250,710; 3,256,186; 3,274,135; and 3,492,231. The book "Lubricant Additives" by M.W. Ranney, published by Noyes Data Corporation of Parkridge, N.J. (1973), discloses a number of overbased metal salts of various sulfonic and carboxylic acids and of phenols which are useful as detergent/dispersants in lubricating oil products. The book also entitled "Lubricant Addi- tives" by C.V. Smallheerand R.K. Smith, published by the Lezius-Hiles Co. of Cleveland, Ohio (1967), similarly 50 discloses a number of overbased sulfonates, phenates and carboxylates which are useful as dispersants. U.S. Patent 4, 100,082 discloses the use of neutral or overbased metal salts of organic sulfur acids, carboxylic acids and phenols as detergent/dispersants for use in fuels and lubricants. U.S. Patent 4,627,928 discloses the use of overbased magnesium salts of substituted aromatic hydroxy carboxylic acids as dispersants, detergents or antioxidants for lubricants and fuels. 55 U.K. Patent 1,242,102 discloses a process comprising contacting at a temperature of at least 20°C, (a) at least one compound selected from inorganic acids, the ammonium, amine and metal salts thereof, and inor- ganic acidic gases (e.g., S02) which, in water, form acids stronger than carbonic acid, and (b) at least one over- based, carbonated Group I or Group II metal-containing complex in the presence of at least one peptizing agent 2 EP 0 586 258 A2 comprising a material which is effective as a dispersing agent in a lubricating oil but which is not an overbased, carbonated, Group I or Group II metal-containing organic complex for a period of time for at least a portion of (a) to react with (b). U.S. Patents 4,507,215 and 4,579,666 disclose a composition comprising: (A) an acidic, neutral or over- based metal salt of (A)(1) at least one acid of the formula 10 wherein each X and X1 is independently oxygen or sulfur, each n is zero or one, and each R1 is independently 15 the same or different hydrocarbon based group, and (A)(ll) at least one carboxylic acid of about 2 to about 40 carbon atoms, the ratio of equivalents of (A)(1) to equivalents of (A)(l I) being in the range of about 0.5:1 to about 1:0; and (B) an olef inically unsaturated compound capable of reacting with active sulfur. Compositions com- prising the foregoing composition reacted with active sulfur are also disclosed. Lubricants and functional fluids comprising the foregoing compositions are disclosed. A process comprising reacting active sulfur with an ole- 20 f inically unsaturated compound in the presence of component (A) is also disclosed. International Publication No. W089/04358 discloses a composition comprising: (A) at least one neutral or overbased metal salt or boron-containing neutral or overbased metal salt of at least one acidic