Patent GB-717039-A (GB)
Title: Improvements in or relating to method of preparing a lubricating oil additive and the new lubricating oil additive resulting from said method
Inventor: BRENNAN ELMER WILLIAM
IPC: C07F9/02
Filed: 1951-07-23
Abstract: A product suitable for use as a lubricating oil additive (see Group III) is obtained by reacting a zinc, barium, calcium, strontium, magnesium, tin, lead, nickel, or cobalt salt of a fatty acid having from 12 to 30 carbon atoms in the molecule and containing a group reactive with a sulphide of phosphorus, with a sulphide of phosphorus and then neutralizing the phospho-sulphurized material with a basic compound of zinc, barium, calcium, strontium, magnesium, tin, lead, nickel, or cobalt, the weight per cent of metal in the neutralized material being substantially greater than that in said salt.  The metal introduced into the phospho-sulphurized fatty acid salt may be the same as or different from the metal present in the salt.  The fatty acid containing a group reactive with a sulphide of phosphorus may be a hydroxy fatty acid, an olefinically unsaturated fatty acid, or an oxidized petroleum fraction containing hydroxy, olefinic and/or keto acids, specified fatty acids being hydroxy stearic acid, oleic acid, ricinoleic acid, wool grease fatty acids and fatty acid mixtures derived from natural oils such as cornseed, rapeseed, linseed, sperm and castor oils.  The fatty acid metal salt starting material may be prepared from the fatty acid or from the oils, fats or waxes which are the sources of the fatty acids; oleic acid may, for example, be neutralized with a metal or a metallic oxide or hydroxide.  The product after phospho-sulphurization is then neutralized with the same or a different metal oxide or hydroxide. An additive having good detergent and anti-oxidant properties can be made by neutralizing the fatty material with barium oxide or hydroxide, phospho-sulphurizing with a phosphorus sulphide, e.g. phosphorus sesquisulphide or pentasulphide and then neutralizing with zinc oxide or hydroxide.  In examples (1) oleic acid dissolved in a hydrocarbon oil and heated to 275-300 DEG  F. is neutralized by the addition of calcium hydroxide and phosphorus sesquisulphide is then added, and reaction effected at 250 DEG  F. whilst passing air into the reaction mixture; the temperature is then raised to 275 DEG  to 300 DEG  F. and barium hydroxide octahydrate then added to the solution and the mixture heated and filtered to yield a product containing phosphorus, sulphur, calcium and barium; (2) calcium oleate is prepared as in (1) and then reacted with phosphorus pentasulphide for two hours at 300 DEG  F., barium hydroxide octahydrate is then added and reaction effected as in (1); (3) wool grease is heated to 300 DEG  to 325 DEG  F. and saponified with barium hydroxide octahydrate, phosphorus sesquisulphide is then added and air passed into the mixture to maintain the temperature at 240 DEG  F.  A hydrocarbon oil is added to the reaction product which is then reacted with barium hydroxide octahydrate at 275 DEG  to 300 DEG F. and the mixture filtered to yield a product containing a high percentage of barium.  Instead of using barium hydroxide to neutralize the phospho-sulphurized barium salt a basic zinc compound may be used.  Other products referred to are the barium salt of the phospho-sulphurized zinc salt of wool grease fatty acids, the products obtained by neutralizing phospho-sulphurized barium oleate with barium oxide or hydroxide or with zinc oxide, and the barium salt of phospho-sulphurized zinc oleate.  Reference is also made to the double lead salts.ALSO:A lubricating oil additive is obtained by reacting a zinc, barium, calcium, strontium, magnesium, tin, lead, nickel, or cobalt salt of a fatty acid having from 12 to 30 carbon atoms in the molecule and containing a group reactive with a sulphide of phosphorus, with a sulphide of phosphorus and subsequently neutralizing the phospho-sulphurized material with a basic compound of zinc, barium, calcium, strontium, magnesium, tin, lead, nickel or cobalt, the weight per cent. of metal in the neutralized material being substantially greater than that in said salt (see Group IV (b)).  The products are useful as additives to enhance detergent properties of mineral lubricating oils.  The metal introduced into the phospho-sulphurized fatty acid salt may be the same as or different from the metal present in the salt. The fatty acid containing a group reactive with a sulphide of phosphorus may be a hydroxy fatty acid, an olefinically unsaturated fatty acid, or an oxidized petroleum fraction containing hydroxy, olefinic and/or keto acids, specified fatty acids being hydroxy stearic acid, oleic acid, ricinoleic acid, wool grease, fatty acids and fatty acid mixtures derived from natural oils such as cornseed, rapeseed, linseed, sperm and castor oils.  An additive having good detergent and antioxidant properties can be made by neutralizing the fatty material with barium oxide or hydroxide, phospho-sulphurizing with a phosphorus sulphide, e.g. phosphorus sesquisulphide or pentasulphide and then neutralizing with zinc oxide or hydroxide.  Stability tests are described for a mid-continent solvent refined oil containing the product obtained by reacting barium hydroxide octahydrate with that obtained by reacting calcium oleate with phosphorus sesquisulphide and with phosphorus pentasulphide respectively, and tests for the detergent qualities of a mid-continent solvent refined oil containing a small amount of a phosphosulphurized terpene together with (a) the barium salt of phospho-sulphurized zinc oleate; or (b) and (c) the product obtained by reacting the barium and zinc salts respectively of wool grease with phosphorus sesquisulphide and then with barium hydroxide octahydrate.  Other additives referred to are the products obtained by neutralizing phospho-sulphurized barium oleate with barium oxide or hydroxide or with zinc oxide.