Patent GB-882295-A (GB)
Title: Amine molybdates and tungstates and lubricating compositions containing them
Inventor: ELLIOTT JOHN SCOTCHFORD
IPC: C10M169/00
Filed: 1959-06-05
Abstract: The invention comprises a lubricating composition comprising a major proportion of a mineral oil of lubricating viscosity and a minor proportion of a salt of a molybdic or tungstic acid with an amine of formula <FORM:0882295/III/1> where R1 and R2 are the same or different straight chain alkyl radicals having up to 4 carbon atoms, and R is an alkyl radical, the total number of carbon atoms in the amine being from 16 to 50 (see Group IV(b) ).  Preferably the composition contains 0,2-5% by weight of the amine salt.  The invention also comprises a lubricating composition comprising a major proportion of a mineral oil of lubricating viscosity and a minor proportion of a combination of two additives, the first being a salt as defined above, and the second being elementary sulphur or an organic divalent sulphur compound soluble in the oil and capable of decomposing at temperatures produced locally by friction under boundary lubricating conditions at metal surfaces to cause the formation of a friction-reducing molybdenum or tungsten compound. The sulphur content of the composition is preferably 0,06-5% by weight. A small proportion, e.g. 0,1-10% by weight of a basic alkaline earth metal petroleum sulphonate may also be present. Specified types of sulphurcontaining compound are oil-soluble metal salts of organic dithiophosphoric acids, organic di- and polysulphides, organic xanthates and thiocarbonates, organic thiocarbamates, organic thiocyanates, organic thioureas, and sulphurized fatty oils or terpenes (which may also be phosphorized).  Other additives may also be present, such as viscosity index improvers (e.g. polybutenes, polymethacrylates), pour point depressants, and antioxidants (e.g. secondary aromatic amines and phenols).  Carbonated basic barium or calcium salts of petroleum sulphonic acids, or metal phenates or phenol sulphides may also be present.  The first Provisional Specification refers also to the use of compositions based on synthetic oils, e.g. synthetic hydrocarbon oils of the alkylene polymer type, dicarboxylic acid diesters, e.g. di-(2-ethylhexyl) sebacate, and ether type lubricants, e.g. polypropylene glycol ethers; to the use of molybdates of primary, secondary or tertiary amines or quaternary ammonium bases (see Group IV(b)); and to the use also of organic mercaptans and thiophenols as the sulphurcontaining compound.  The second Provisional Specification refers to the use of molybdates and tungstates of amines of formula <FORM:0882295/III/2> where R is a saturated alkyl radical having at least 13 carbon atoms, R1 and R2 are hydrogen, alkyl or cycloalkyl, and R3 and R4 are lower alkyl radicals (see Group IV(b)); and to the use, as an alternative to the divalent sulphur compound, of selenium or tellurium compounds, and specifies di-n-butyl diseleno diacetate, tri-n-butyl selenophosphate, and tri-n-butyl tellurophosphate.ALSO:The invention comprises salts of a molybdic or tungstic acid with an amine of formula:  <FORM:0882295/IV (b)/1> where R1 and R2 are the same or different straight chain alkyl radicals containing up to 4 carbon atoms, and R is an alkyl radical, the total number of carbon atoms in the amine being from 16 to 50; preferably R1 and R2 are both methyl. The salts are prepared by heating the amine and molybdic acid or ammonium tungstate in the presence of water, and removing excess water and isolating the salt.  Molybdates may be prepared by heating equivalent amounts of the amine, which may be dissolved in a mineral oil, and molybdic acid at 50 DEG C.-80 DEG C. in the presence of water, stirring to dissolve the molybdic acid, and subsequently removing the water.  Tungstates may be prepared by heating equivalent amounts of the amine and ammonium tungstate in the presence of aqueous ammonia under reflux while passing a stream of nitrogen through the reaction mixture until the reaction is substantially complete, distilling water and ammonium from the mixture, and drying the product by blowing nitrogen through it at a temperature of about 100 DEG C.  Specified salts are Primene JM-T molybdate, paramolybdate and tungstate, t-octadecylamine molybdate and tungstate, and t-eicosylamine, 1-methyl-1-ethyl octadecylamine, 1,1-dimethyl octadecylamine, 1 - methyl - 1 - butyl hexadecyl - amine and t-triacontylamine molybdates.  The first Provisional Specification refers to molybdates of primary, secondary or tertiary amines or of quaternary ammonium bases, and specifies oleylamine, t-octylamine, dioleylamine, olein dimethylamine, cetyl pyridinium, octadecyl trimethylammonium and Primene JM-T formaldimine molybdates.  The second Provisional Specification refers to molybdates and tungstates of amines of formula:  <FORM:0882295/IV (b)/2> where R is a saturated alkyl radical having at least 13 carbon atoms, R1 and R2 are hydrogen, alkyl or cycloalkyl radicals, and R3 and R4 are lower alkyl radicals, and specifies N-methyl Primene JM-T, N-dimethyl Primene JM-2, t-octadecylamine and t-eicosylamine molybdates and Primene JM-T tungstate.  The amine molybdates and tungstates are oil additives (see Group III).