Patent GB-774683-A (GB)
Title: Improvements in or relating to lubricating compositions
IPC: C10M159/20
Filed: 1953-11-03
Abstract: Polyisobutylene, or the chlorination product thereof, is heated with phosphorus sulphide and sulphur, PCl3 and sulphur, or with PSCl3, and the resulting acid or the barium salt thereof converted to a substantially neutral barium carbonate complex by treatment in the presence of mineral oil, t-butyl phenol and one or more barium sulphonates (chosen from barium salts of mahogany sulphuric acid, white oil sulphonic acid and diisododecyl benzene sulphonic acid), with barium oxide and water and then blowing with carbon dioxide. Alternatively, a calcium salt of the high molecular weight phosphorus acid is treated in the presence of mineral oil, phenol and calcium mahogany sulphonate or di-isodecyl benzene sulphonic acid, with calcium hydroxide and water and then blown with carbon dioxide to produce a substantially neutral calcium carbonate complex. Lubricating compositions (see Group III) are formed from lubricating oil, at least one alkaline earth carbonate complex, as above, and at least one phosphosulphurized organic material derived from an unsaturated hydrocarbon, aromatic hydrocarbon, alcohol or phenol.ALSO:Lubricating compositions (see Group III) contain (a) at least one substantially neutral alkaline earth metal carbonate complex and (b) at least one phosphosulphurized organic material. Ingredient (a) is derived from at least one oil-soluble organic compound which contains at least 12 carbon atoms in the molecule and which is chosen from the aliphatic and cyclic sulphur acids and phosphorus acids, the thio acids corresponding to such acids, and the alkaline earth metal salts of any of these acids, the ratio of equivalents of carbonate to oil-soluble organic acid normal salt in ingredient (a) being not less than 0.1 and not substantially more than 10.  In addition, ingredient (a) is such that a solution thereof in an equal weight of mineral lubricating oil has a neutralization value (as measured by ASTM Test D-974-48T) not substantially more than 20 and, when converted to a 1 per cent by weight aqueous dispersion at 25 DEG  C., has a pH of 5-9.  Ingredient (b) is derived from an unsaturated hydrocarbon, aromatic hydrocarbon, alcohol or phenol by a process which involves reaction with a phosphorus sulphide, and contains at least one P = S linkage in the molecule. The oil-soluble compound containing at least 12 carbon atoms in the molecule, from which ingredient (a) is derived may be an aliphatic or cyclic sulphonic, sulphamic, sulphinic, thiosulphonic, phosphorous, phosphoric, thiophosphoric, thiophosphorous, phosphinic, phosphonic, thiophosphinic or thiophosphonic acid, or an acidic material obtained by treating an aliphatic and/or aromatic hydrocarbon with a phosphosulphurizing reagent.  Mixtures of such acids may be employed, for example mixtures of sulphonic acids or mixtures of a sulphonic acid with a phosphorus acid.  Several sulphonic acids are referred to and these include phenol sulphonic acid, diphenyl ether sulphonic and disulphonic acids, diphenyl amine sulphonic and disulphonic acids, alpha-chloronaphthalene sulphonic acid, cetyl phenol sulphonic and disulphonic acids, thiophene sulphonic acid, naphthalene disulphide sulphonic and disulphonic acids, cetyl phenol disulphide sulphonic acids, di-capryl nitro-naphthalene sulphonic acids, nitroso-paraffin wax sulphonic acids, and cetyl phenol monosulphide sulphonic acids. In the preparation of ingredient (a), the acid and/or an alkaline earth metal salt thereof may be treated with a large amount of alkaline earth metal base, for example in the presence of a promoter (e.g. phenol, beta-naphthol, p-tert. butyl phenol, isononyl phenol, tert.-octyl phenol, tert.-butyl mono- or di-chlorophenol, 1-(p - nitrophenyl) - 2 - nitrobutane, gammanitromethyl hexoate, 1-chloro-1-nitro-propane, isophorone oxime, o-chlorobenzamide, ethyl acetoacetate, benzoylacetone or acetyl acetone), and the mass then carbonated.  Alternatively, a basically-reacting alkaline earth metal complex may be prepared and rendered substantially neutral by carbonation.  Carbonation may be effected by treatment with carbon dioxide or carbon dioxide-yielding reagents such as ammonium carbonate or urea.  In examples, barium mahogany sulphonate, usually in mineral oil solution, is treated with barium oxide and water, and the product is blown with carbon dioxide until substantially neutral. The treatment with barium oxide and water may be carried out in the presence of additional organic phosphorus or sulphur acids or their salts, for example di-isobutenyl sulphonic acid, di-isopropyl benzene sulphonic acid, di-isononyl naphthalene sulphonic acid, tert. butyl naphthalene sulphonic acid, tris-tert. octyl diphenyl ether sulphonic acid, methyl naphthalene sulphonic acid, trichloro-diphenyl ether sulphonic acid, cymene sulphonic acid, barium petrolatum sulphonate, barium di-isododecyl benzene sulphonate, di-isopropyl dithiophosphoric acid, dieicosyl monothiophosphate, eicosyl phosphonic acid, dieicosyl phosphinic acid, bis-(tri-tert. amyl phenyl) dithiophosphinic acid, di-(2-ethyl hexyl) phosphoric acid, P2S5-treated nonene, P2S5-treated iso-octadecene, P2S5-treated aromatic petroleum fraction, barium salt of P2S5-treated paraffin wax-substituted naphthalene, PSCl3-treated diphenyl ether, PSCl3-treated chlorinated paraffin wax, and mixtures of barium di-isododecyl benzene sulphonate with dihydro - abietyl monothiophosphate, P2S5-treated dehydrochlorinated chlorinated paraffin wax, PSCl3-treated alpha-methyl naphthalene or PSCl3-treated isononyl phenol.  Instead of barium mahogany sulphonate, there may be employed barium white oil sulphonate, barium salt of paraffin wax-substituted naphthalene sulphonic acid, barium di-isododecyl benzene sulphonate, calcium mahogany sulphonate, paraffin wax-substituted phenol sulphonic acid, petroleum sulphonic acid, di-(2-ethyl-hexyl) monothiophosphoric acid or di-(n-hexyl) dithiophosphoric acid.  Instead of barium oxide, there may be employed strontium oxide or calcium hydroxide. As regards the preparation of ingredient (b), details are given of the reaction of P4S7 with n-octene-1, iso-octene, di-isobutylene (in the presence of oleic acid or the subtance known under the Registered Trade Mark "Loro"), caprylene, dipentene (in the presence of P4S5), hexadecene-1, cetene-1, dehydrochlorinated chlorinated kerosene or paraffin wax, turpentine, tri-isobutylene, capryl alcohol (in the presence of oleic acid) and oleyl alcohol; the reaction of P2S5 with turpentine; and the reaction of P4S3 with dehydrochlorinated chlorinated paraffin wax or capryl alcohol.ALSO:A lubricating composition, especially suitable for use in the crankcase of an internal combustion engine operating under severe conditions, comprises a lubricating oil having dissolved therein (a) at least one substantially neutral alkaline earth metal carbonate complex and (b) at least one phosphosulphurized organic material.  Ingredient (a) is derived from at least one oil-soluble organic compound which contains at least 12 carbon atoms in the molecule and which is chosen from the aliphatic and cyclic sulphur acids and phosphorus acids, the thio acids corresponding to such acids, and the alkaline earth metal salts of any of these acids, the ratio of equivalents of carbonate to oil soluble organic acid normal salt in ingredient (a) being not less than 0.1 and not substantially more than 10.  In addition, ingredient (a) is such that a solution thereof in an equal weight of mineral lubricating oil has a neutralization value (as measured by ASTM Test D-974-48T) not substantially more than 20 and, when converted to a 1 per cent by weight aqueous dispersion at 25 DEG C., has a pH of 5-9. Ingredient (b) is derived from an unsaturated hydrocarbon, aromatic hydrocarbon, alcohol or phenol by a process which involves reaction with a phosphorus sulphide and contains at least one P=S linkage in the molecule.  Included among the examples of ingredient (b) are esters and ester-salts of inorganic thioacids of phosphorus.  The proportion of ingredient (a) in the lubricating composition yields 1 part by weight of alkaline earth metal sulphate ash while the proportion of ingredient (a) contains 0.0025-1.5 parts by weight phosphorus.  The lubricating oil may be of synthetic, vegetable or mineral origin, but petroleum oils are preferred.  The lubricating composition may contain additional ingredients such as detergents, corrosion inhibitors, oxidation inhibitors, foam inhibitors (e.g. silicones), pour depressants, viscosity index improving agents (e.g. copolymers of methyl alpha-lauryl acrylate and methyl alpha-isobutyl methacrylate) and odour improving agents.  Numerous examples of ingredients (a) and (b), of their preparation (see Groups IV(a) and IV(b)), and of mineral lubricating oil compositions containing ingredients (a) and (b), are given; the mineral lubricating oil composition in general contain alkaline earth metal sulphonate-carbonate complexes as ingredients (a) and phospho-sulphurized hydrocarbons or zinc dialkyl dithiophosphates as ingredient (b).