Patent GB-700578-A (GB)
Title: Improvements in or relating to lubricants and lubricant additives
Inventor: MUSSELMAN JOHN MYERS
Filed: 1951-08-22
Abstract: The invention comprises products made by heating a mixture of an olefine hydrocarbon, a non-metallic oxygen-containing organic compound and a phosphorus sulphide.  The products may be converted to their metal or nitrogen base salts by heating with a basic metal compound or an organic nitrogen base or ammonia or esterified by heating with an alcohol or a thio-alcohol.  P2 S5 is preferred, and mixtures of phosphorus sulphides may be used.  The olefine is preferably a poly-olefine.  "Motor polymer," a product made from C3 and C4 olefines by non-selective polymerisation, boiling within the range 80 - 500 DEG F., with a major portion of boiling range 120 - 400 DEG F., "reduced motor polymer" a motor polymer from which a polymer gasoline fraction has been removed by distillation to 250 DEG F. of average molecular weight about 145 and preferably containing a major amount of branched chain olefines boiling below 500 DEG F. or a poly-isobutylene viscosity index improver may be used.  The non-metallic oxygen - containing compound may contain hydroxyl, carbonyl or ether oxygen.  Preferably it should boil at a temperature above that of the reaction, which may be effected under pressure. Representative of many specified non-metallic oxygen-containing compounds are:-lanolin, sperm oil, hydrogenated butyl stearate, stearic acid, methyl chloronaphthenate, dichloropalmitic acid, babassu oil, ethylene glycol mono ethers, diglycol chlorohydrin, lauryl alcohol, n - octanol oleic and benzoic acid, dihydroxybenzoic acid, dipentadecyl ketone, diamyl phenol, hydrogenated methyl ester of rosin, degras, palmitone and oxidised wax or kerosene.  Diluents e.g. white oil and mineral lubricating oils may be present during the reaction, and an inert gas e.g. N2 or H2S, may be present during reaction.  Temperatures of 200 - 500 DEG F., are mentioned.  The final product is preferably centrifuged or filtered to remove sludge and may be solvent extracted or contacted with an absorbent.  S, Se or Te may be incorporated into the final product.  S may be incorporated by adding elementary S or a compound which yields S simultaneously with, or after the formation and cooling of the primary reaction product; if after, then at about 200-300 DEG F., Se and Te may similarly be incorporated. Metal salts are formed from one or more basic metal compounds e.g. sulphides, oxides, hydroxides, carbides and cyanamides. Group I, II and III metals are preferred e.g. K, Zn, Ba and Al. Salts of heavier metals, e.g. Cr, Cd, Sn, Pb, Sb, Bi and As may have particular uses.  Metal or nitrogen base salts or esters containing subsequently added S may be made either by reacting the first product with an element of the S family and converting to the salt, or the salt of the first product may be reacted with the S family element.  Metal salts may be made at about 100 - 350 DEG F.  Nitrogen bases mentioned are ammonia, amines and heterocyclic nitrogen bases, and for ester formation alkyl, aryl, cycloalkyl and heterocyclic compounds containing an alcoholic or thioalcoholic group may be used at temperatures of about 100 - 350 DEG F.  Advantageously water is present when the metal or nitrogen base salt is formed and may be introduced as water of crystallisation or as a hydrate of the metal compound or of the nitrogen base, or added separately.  A plurality of metals or of nitrogen bases or esterifying agents or mixtures thereof may be used and the final product need not be completely converted into a salt or ester. Products with P2 S5 and the following mixtures are mentioned:-reduced motor polymer and cyclohexanol or beeswax and motor polymer and diamyl phenol and also a product from P4 S7 and motor polymer and coconut oil.  The n-amyl, n-octyl or lauryl ester or thio - ester and the n - amylamine, aniline or triethanolamine base salts of any of the above reaction products are also mentioned and their K, Ba, Cr and Ca salts.  The products are used as lubricating oil additives (see Group III), and are also antioxidants for e.g. elastomers, plastic materials, waxes, coating materials, paints, fats, fatty oils and gasoline.ALSO:The invention comprises products made by heating a mixture of an olefine hydrocarbon, a non-metallic oxygen-containing organic compound and a phosphorus sulphide.  The products may be converted to their metal or nitrogen base salts by heating with a basic metal compound or an organic nitrogen base or ammonia or esterified by heating with an alcohol or a thio-alcohol. Diluents, e.g. white oil and mineral lubricating oil may be present during the reaction.  5 - 60, usually 10-50, especially 15-35, weight per cent. of the sulphide based on the weight of the mixture may be used.  P2S5 is preferred.  Mixtures of phosphorus sulphides may be used.  The olefine particularly contains 6-25 C atoms and is preferably a poly-olefine.  "Motor polymer," a product made from C3 and C4 olefines by non selective polymerization, boiling within the range 80-500 DEG F., with a major portion of boiling range 120-400 DEG F., "reduced motor polymer" a motor polymer from which a polymer gasoline fraction has been removed by distillation to 250 DEG F. of average molecular weight about 145 and preferably containing a major amount of branched chain olefines boiling below 500 DEG F. and a poly-isobutylene viscosity index improver are specified olefines. Preferably olefines soluble or dispersible in lubricating oils are used since the products are used as lubricating oil additives (see Group III).  The non-metallic oxygen containing compound may contain hydroxyl, carboxyl or ether oxygen.  Preferably it should boil at a temperature above that of the reaction which may be effected under pressure.  Representative of many specified non-metallic oxygen-containing compounds are lanolin, sperm oil, p  butyl stearate, methyl chloronaphthenate, dichloropalmitic acid, babassu oil, ethylene glycol mono ethers, diglycol chlorohydrin, lauryl alcohol, oleic and benzoic acid, dihydroxybenzoic acid, palmitone and oxidized wax or kerosene.  Equal weight ratios of hydrocarbon and oxygen-compound are suitable and proportions of 10 - 70 parts of oxygen-compound to 90 - 30 parts of hydrocarbon are preferred.  An inert gas, e.g. N2 or H2S, may be present during reaction. Temperatures of 200-500 DEG F., preferably 250-300 DEG F., are mentioned.  The final product is preferably centrifuged or filtered to remove sludge and may be solvent extracted or contacted with an absorbent.  S, Se or Te may be incorporated into the final product. S may be incorporated by adding elementary S or a compound which yields S, e.g. treating the sulphide derived reaction product therewith or its metal or nitrogen base salts therewith.  When additional S is to be present about 0.01 - 2.0, preferably 0.1 - 1.0, gm. atoms of S per mol. of the phosphorus sulphide used is incorporated by adding elementary S, e.g. simultaneously with, or after the formation and cooling of the primary reaction product; if after, then at about 200-300 DEG F. Se and Te may similarly be incorporated.  The metal salts are formed from one or more basic metal compounds, e.g. sulphides, oxides, hydroxides, carbides and cyanomides.  Group I, II, and III metals are preferred, e.g. K, Zn, Ba and Al.  Salts of heavier metals, e.g. Cr., Cd, Sn, Pb, Sb, Bi and As may have particular uses.  Metal or nitrogen base salts or esters containing subsequently added sulphur may be made either by reacting the first product with an element of the S family and converting to the salt or the salt of the first product may be reacted with the S family element.  Metal salts may be made at about 100 - 350 DEG F., preferably about 180 - 250 DEG F.  About 0.25 - 6.0 preferably about 1.0 - 3.0, equivs. of metal compound may be used per mol. of sulphide.  Nitrogen bases mentioned are ammonia amines and heterocyclic nitrogen bases.  About 0.25 - 6.0, preferably about 1-4, equivs. of nitrogen base are used per mol. of sulphide.  For ester formation alkyl, aryl, cycloalkyl and heterocyclic compounds containing an alcoholic or thioalcoholic group may be used at temperatures of about 100 - 350 DEG F., preferably 180 - 280 DEG F., about 0.2 - 6.0, preferably about 1.0 - 4.0 equivs of esterifying agent being used per mol of sulphide.  Advantageously water is present when the metal or nitrogen base salt is formed and may be introduced as water of crystallization, or as a hydrate of the metal compound or of the nitrogen base, or added separately.  A plurality of metals or of nitrogen bases or esterifying agents or mixtures thereof may be used and the final product need not be completely converted into a salt or ester.  Products with P2 S5 and the following mixtures are mentioned:-reduced motor polymer and cyclohexanol or beeswax, cetene-1 and glycerol stearate, octene-2 and degras, penta-decene - 3 and cetyl alcohol, highly cracked hydrocarbon stock and palmitone or methyl stearate, C5 - C12 mono-olefines and sperm oil or cyclohexanone, motor polymer and diamyl phenol, C8 - C16 mono - olefines and mixed stearic and oleic acids, and also a product from P4 S7 and motor polymer and coconut oil.  The n - amyl, n - octyl or lauryl ester or thio-ester and the n-amylamine, aniline or triethanolamine base salts of any of the above reaction products are also mentioned and their K, Ba, Cr and Ca salts.  The products are also antioxidants for, e.g. elastomers, plastic materials, waxes, coating materials, paints, fats, fatty oils and gasoline.  In examples, P2 S5 and reduced motor polymer are reacted in (1a), (2a), (2b), and (3) - (6) with hydrogenated sperm oil and the product of (1a) reacted in (1b) with potassium hydroxide and water and (1c) barium hydroxide octahydrate (7) stearic acid, (8) babassu oil, (9) lauryl alcohol, (10) n - octanol, (11) dipentadecyl ketone, (12) an oxidized petroleum fraction; (13) diamylphenol, (14) hydrogenated methyl