Patent GB-663881-A (GB)
Title: Extreme pressure lubricant additives and lubricants containing them
Filed: 1949-01-24
Abstract: A lubricant additive is obtained by sulphurizing and phosphorizing an ester comprising an aliphatic glycol, polyglycol, thioglycol or polythioglycol esterified with a mixture of an unsaturated fatty acid or acids and a rosin acid or acids.  The preferred esters may generally be represented by the formul  RCOX - ( - CHZ - CHZ1 - X)n - OCR1 or RCOX - ( - CHZ - CHZ1 - )n - XOCR1 in which X is oxygen or sulphur, n is an integer from 1 to 4, R and R1 are respectively the hydrocarbon radicals of the unsaturated fatty acid and rosin acid and Z and Z1 are hydrogen or C1 to C4 alkyl groups.  Some of the ester molecules may be diesters of the fatty acids and others diesters of the rosin acids, depending on the relative proportions and reactivities of the fatty and rosin acids used.  Preferably R, R1 contains 11 to 21 carbon atoms.  Suitable glycols specified are ethylene, diethylene, triethylene, propylene, dipropylene and butylene glycols and monothioethylene and dithioethylene glycols. The fatty acids include oleic, linoleic, linolenic and ricinoleic acids and as rosin acids there may be used naturally-occurring mixtures or separated individual acids or mixtures thereof such as abietic, neobietic, or dehydroabietic acids.  Tall oil is a convenient source of the mixed acids used in the esterification. The esterification may be carried out using the mixed acids or in two stages, e.g. the glycol being half esterified with a rosin acid or acids in a first stage and the half ester then fully esterified with the unsaturated fatty acid or acids.  The ester is then sulphurized and phosphorized.  In one modification, the ester is first reacted with elemental sulphur, e.g. by heating at above 250 DEG  F. and a sulphurization catalyst such as sulphur chloride or sulphur dichloride may be added.  The sulphurized product is then phosphorized, e.g. by reaction with a bi-elemental phosphorus compound, e.g. P4S3, P4S7, P2S5, PCl3, PCl5 and P2O5. The phosphorizing reaction with phosphorus sulphides may be effected at temperatures of 150-300 DEG  F.  In another modification the sulphurization and phosphorization is effected simultaneously by reacting the ester with a sulphide of phosphorus or with a mixture of sulphur and a bi-elemental phosphorus compound.  In this case the reactants are preferably heated to 150-250 DEG  F. for 2-5 hours and then to a higher temperature, e.g. 300-400 DEG  F., for several hours or until a product is obtained which in 10 per cent by weight concentration in mineral oil does not blacken copper when heated at 250 DEG  F. for one hour.  In examples: (1), (2) and (3) an ethylene glycol ester of tall oil is reacted with sulphur and the mixture then cooled.  The sulphurized product is then reacted with P4S3 at elevated temperatures; (4) a similar ester is prepared by first preparing the half ester of mixed rosin acids from rosin and ethylene glycol followed by further esterification with oleic acid and this ester is sulphurized and then phosphorized as in the preceding examples. The products of the examples are blended with a mineral lubricating oil and the properties of the compositions as lubricants are described.  The additives may be used in hydrocarbon lubricating oils or in synthetic lubricating oils, e.g. those of the ester or polyether type, in cutting oils and in soluble cutting oils in conjunction with emulsifying agents such as sodium sulphonates.  They may also be used with conventional additives such as thickeners, oiliness agents, oxidation inhibitors, tackiness agents, viscosity index improvers and pour-point depressants, and the additives of the invention may also be used in greases thickened  with soaps, carbon blacks, silica gel and other known grease-forming materials. According to the Provisional Specification the radicals R and R1 in the above ester formula may be aliphatic or cyclic and at least one of the radicals must contain an ethylenic bond and the acids used to form the glycol esters are stated to include the hydrogenation products of naturally occurring rosin and tall oils.ALSO:A lubricant additive is obtained by sulphurizing and phosphorizing an ester comprising an aliphatic glycol, polyglycol, thioglycol or polythioglycol esterified with a mixture of an unsaturated fatty acid or acids and a rosin acid or acids.  The preferred esters may generally be represented by the formul  <FORM:0663881/IV (b)/1> in which X is oxygen or sulphur, n is an integer from 1 to 4, R and R1 are respectively the hydrocarbon radicals of the unsaturated fatty acid and rosin acid and Z and Z1 are hydrogen or C1 to C4 alkyl groups.  Some of the ester molecules may be diesters of the fatty acids and others diesters of the rosin acids, depending on the relative proportions and reactivities of the fatty and rosin acids used.  Preferably R contains 11 to 21 carbon atoms.  Suitable glycols specified are ethylene, diethylene, triethylene, propylene, dipropylene and butylene glycols and monothioethylene and dithioethylene glycols. The fatty acids include oleic, linoleic, linolenic and ricinoleic acids and as rosin acids there may be used naturally occurring mixtures or separated individual acids or mixtures thereof-such as abietic, neoabietic, or dehydroabietic acids.  Tall oil is a convenient source of the mixed acids used in the esterification. The esterification may be carried out using the mixed acids or in two stages, e.g. the glycol being half esterified with a rosin acid or acids in a first stage and the half ester then fully esterified with the unsaturated fatty acid or acids.  The ester is then sulphurized and phosphorized.  In one modification the ester is first reacted with elemental sulphur, e.g. by heating at above 250 DEG  F. and a sulphurization catalyst such as sulphur chloride or sulphur dichloride may be added.  The sulphurized product is then phosphorized, e.g. by reacting with a bi-elemental phosphorus compound, e.g. P4S3, P2S5, Pcl3, PCl5 and P2O5.  The phosphorizing reaction with phosphorus sulphides may be effected at temperatures of 150 DEG  to 300 DEG  F.  In another modification the sulphurization and phosphorization is effected simultaneously by reacting the ester with a sulphide of phosphorus or with a mixture of sulphur and a bi-elemental phosphorus compound.  In this case the reactants are preferably heated to 150 DEG  to 250 DEG  F. for 2-5 hours and then to a higher temperature, e.g. 300-400 DEG  F., for several hours or until a product is obtained which in 10 per cent by weight concentration in mineral lubricating oil does not blacken copper when heated at 250 DEG  F. for one hour.  In examples: (1), (2) and (3), an ethylene glycol ester of tall oil is reacted with sulphur and the mixture then cooled.  The sulphurized product is then reacted with P4S3 at elevated temperature; (4) a similar ester is prepared by first preparing the half ester of mixed rosin acids from rosin and ethylene glycol followed by further esterification with oleic acid and this ester is sulphurized and then phosphorized as in the preceding examples. According to the Provisional Specification the radicals R and R1 in the above ester formula may be aliphatic or cyclic and at least one of the radicals must contain an ethylenic bond and the acids used to form the glycol esters are stated to include the hydrogenation products of naturally occurring rosin and tall oils.ALSO:A lubricating composition comprises a lubricating oil and a minor proportion by weight of a product obtained by sulphurizing and phosphorizing an ester comprising an aliphatic glycol, polyglycol, thioglycol or polythioglycol esterified with a mixture of an unsaturated fatty acid or acids and a rosin acid or acids.  The preferred esters may generally be represented by the formulae: RCOX-(-CHZ-CHZ1-X)n-OCR1 or RCOX-(CHZ-CHZ1-)n-XOCR1 in which X is oxygen or sulphur, n is an integer from 1 to 4, R and R1 are respectively the hydrocarbon radicals of the unsaturated fatty acid and rosin acid and Z and Z1 are hydrogen or C1 to C4 alkyl groups.  Some of the ester molecules may be diesters of the fatty acids and others diesters of the rosin acids depending on the relative proportions and reactivities of the fatty and rosin acids used.  Preferably R contains 11 to 21 carbon atoms.  Suitable glycols specified are ethylene, diethylene, triethylene, propylene, dipropylene and butylene glycols and monothioethylene and dithioethylene glycols.  The fatty acids include oleic, linoleic, linolenic and ricinoleic acids and as rosin acids there may be used naturally occurring mixtures or separated individual acids or mixtures thereof such as abietic, neobietic, or dehydroabietic acids. Tall oil is a convenient source of the mixed acids used in the esterification.  The esterification may be carried out using the mixed acids or in two stages, e.g. the glycol being half esterified with a rosin acid or acids in a first stage and the half ester then fully esterified with the unsaturated fatty acid or acids.  The ester is then sulphurized and phosphorized.  In one modification the ester is first reacted with elemental sulphur, e.g. by heating at above 250 DEG F and a sulphurization catalyst such as sulphur chloride or sulphur di-chloride may be added.  The sulphurized product is then phosphorized, e.g. by reaction with a bi-elemental phosphorus compound, e.g. P4S3, P4S7, P2S5, PC15 and P2O5.  The phosphorizing reaction with phosphorus sulphides may be effected at temperatures of 150 DEG -300 DEG F.  In another modification the sulphurization and phosphorization is effected simultaneously by reacting the ester with a sulphide of phosphorus or with a mixture of sulphur and a bielemental phosphorus compound.  In this case the reactants are preferably heated to 150 DEG -250 DEG F for 2-5 hours and then to a higher temperature, e.g. 300 DEG -400 DEG F for several hours or until a product is obtained whic