Patent GB-965325-A (GB)
Title: High barium-content carbonated salts of phosphorus sulfidehydrocarbon products and method for preparing the same
IPC: C07F9/04
Filed: 1962-10-02
Abstract: A salt of a phosphorus sulphide-hydrocarbon reaction product having a barium to phosphorus weight ratio greater than 6 (e.g. up to 36) and finding application as a detergent in lubricating oil compositions is prepared by (1) forming a reaction mixture comprising (a) a hydrocarbon solution of the phosphorus sulphide-hydrocarbon reaction product, (b) a methanol solution of barium methylate containing from 20 to 40 mols. of methanol per mol. of barium, in an amount to supply to the reaction mixture an excess of barium methylate over that required to form a normal barium salt of said phosphorus sulphidehydrocarbon reaction product and (c) water, in an amount to supply to said reaction mixture from 2 to 4 mols. of water per mol. of barium supplied by the barium methylate solution, (2) heating the reaction mixture at 65 DEG C. to 200 DEG C. whereby a basic barium salt is formed, (3) contacting with carbon dioxide gas at 90 DEG C. to 200 DEG C. to incorporate into said basic barium salt 0.3 parts by weight of carbon dioxide per part of basic barium present in said salt, (4) lowering to below 65 DEG C., (5) adding additional methanol solution of barium methylate and water in amount to supply from 0.25 to 4 parts by weight of barium per part of phosphorus supplied to the reaction mixture in step (1) by the phosphorus sulphide-hydrocarbon reaction product, the mol. proportions of methanol and water to barium being within the same limits as in step (1), (6) again heating the reaction mixture at 65 DEG C. to 200 DEG C. and (7) filtering the reaction mixture to recover a hydrocarbon solution of the high barium-content salt of the phosphorus sulphidehydrocarbon reaction product. Steps (3) to (6) may be repeated in order to incorporate additional amounts of barium. In examples, (1) (a) comprises a paraffin oil solution of a hydrolysed propylene polymer/P2S5 reaction product, and the description also illustrates the application of the product of the invention in a Mid-Continent oil, SAE 30, also containing zinc dialkyl dithiophosphate as antioxidant.  Other hydrocarbons which may be used in forming the initial reaction product are polymers and copolymers of butylenes and amylenes and the hydrocarbons disclosed in U.S.A.  Specifications 2,316,080, 2,316,082, 2,316,088 and 2,806,022.ALSO:A salt of a phosphorus sulphide-hydrocarbon reaction product having a barium to phosphorus weight ratio greater than 6 (e.g. up to 36) and finding application as a detergent in lubricating oil compositions is prepared by (1) forming a reaction mixture comprising (a) a hydrocarbon solution of the phosphorus sulphide-hydrocarbon reaction product, (b) a methanol solution of barium methylate containing from 20 to 40 mols of methanol per mol of barium, in an amount to supply to the reaction mixture an excess of barium methylate over that required to form a normal barium salt of said phosphorus sulphide-hydrocarbon reaction product and (c) water, in an amount to supply to said reaction mixture from 2 to 4 mols of water per mol of barium supplied by the barium methylate solution, (2) heating the reaction mixture at 65 DEG C. to 200 DEG C. whereby a basic barium salt is formed, (3) contacting with carbon dioxide gas at 90 DEG C. to 200 DEG C. to incorporate into said basic barium salt 0.3 parts by weight of carbon dioxide per part of basic barium present in said salt, (4) lowering to below 65 DEG C., (5) adding additional methanol solution of barium methylate and water in amount to supply from 0.25 to 4 parts by weight of barium per part of phosphorus supplied to the reaction mixture in step (1) by the phosphorus sulphide-hydrocarbon reaction product, the mol proportions of methanol and water to barium being within the same limits as in step (1), (6) again heating the reaction mixture at 65 DEG C. to 200 DEG C. and (7) filtering the reaction mixture to recover a hydrocarbon solution of the high barium-content salt of the phosphorus sulphide-hydrocarbon reaction product.  Steps (3) to (6) may be repeated in order to incorporate additional amounts of barium.  In examples, (1) (a) comprises a paraffin oil solution of a hydrolyzed propylene polymer/P2S5 reaction product, and the description also illustrates the application of the product of the invention in a Mid-Continent oil, SAE 30, also containing zinc dialkyl dithiophosphate as antioxidant.  Other hydrocarbons which may be used in forming the initial reaction product are polymers and copolymers of butylenes and amylenes and the hydrocarbons disclosed in U.S.A Specifications 2,316,080, 2,316,082, 2,316,088 and 2,806,022.ALSO:A salt of a phosphorus sulphide-hydrocarbon reaction product having a barium to phosphorus weight ratio greater than 6 (e.g. up to 36) and finding application as a detergent in lubricating oil compositions is prepared by (1) forming a reaction mixture comprising (a) a hydrocarbon solution of the phosphorus sulphide-hydrocarbon reaction product, (b) a methanol solution of barium methylate containing from 20 to 40 mols. of methanol per mol. of barium, in an amount to supply to the reaction mixture an excess of barium methylate over that required to form a normal barium salt of said phosphorus sulphide-hydrocarbon reaction product and (c) water, in an amount to supply to said reaction mixture from 2 to 4 mols. of water per mol. of barium supplied by the barium methylate solution, (2) heating the reaction mixture at 65 DEG  to 200 DEG  C. whereby a basic barium salt is formed, (3) contacting with carbon dioxide gas at 90 DEG  to 200 DEG  C. to incorporate into said basic barium salt 0.3 parts by weight of carbon dioxide per part of basic barium present in said salt, (4) lowering to below 65 DEG  C., (5) adding additional methanol solution of barium methylate and water in amount to supply from 0.25 to 4 parts by weight of barium per part of phosphorus supplied to the reaction mixture in step (1) by the phosphorus sulphide-hydrocarbon reaction product, the mol. proportions of methanol and water to barium being within the same limits as in step (1), (6) again heating the reaction mixture at 65 DEG  to 200 DEG  C. and (7) filtering the reaction mixture to recover a hydrocarbon solution of the high barium-content salt of the phosphorus sulphide-hydrocarbon reaction product.  Steps (3) to (6) may be repeated in order to incorporate additional amounts of barium. In examples: (1) (a) comprises a paraffin oil solution of a hydrolysed propylene polymer/P2S5 reaction product, and the description also illustrates the application of the product of the invention in a Mid-Continent oil, SAE 30, also containing zinc dialkyl dithiophosphate as antioxidant.  Other hydrocarbons which may be used in forming the initial reaction product are polymers and copolymers of butylenes and amylenes and the hydrocarbons disclosed in U.S.A. Specifications 2,316,080, 2,316,082, 2,316,088 and 2,806,022.