Patent GB-754871-A (GB)
Title: Improvements in or relating to phosphorus and sulfur-containing oil additives
IPC: F02B3/06
Filed: 1954-04-30
Abstract: Additive compounds for mineral oils are obtained by reacting a mineral oil with a phosphorus sulphide in the presence of 5 per cent to 25 per cent by weight, based on the total hydrocarbon oil blend, of a wax-free and asphalt-free petroleum resin having an S.U.S. viscosity at 210 DEG  F. of at least 800 and which has been solvent precipitated from a paraffinic-type petroleum oil residuum, whereby the sulphur content of the phosphosulphurized mineral oil is more than 6 per cent by weight.  The petroleum resin may be precipitated from a residual paraffinic oil which has been dewaxed and de-asphalted if necessary by treatment with a liquefied normally gaseous hydrocarbon, e.g. propane, and should preferably have a Saybolt viscosity at 210 DEG  F. of 1000 to 4000 seconds or more and a molecular weight above 1000.  The mineral oil used should preferably have an S.U.S. viscosity at 210 DEG  F. of about 40 to 300 and may be obtained from Pennsylvania crudes, or Midcontinent crudes such as Panhandle crudes.  When the mineral oil is a bright stock containing naturally occurring resins additional resins should be added thereto to bring the total amount of resin to within 5 to 25 per cent based on the total oil blend.  Specified phosphorus sulphides are P2S3, P4S3, P4S7 and P2S5, the phosphosulphurization being carried out at elevated temperature, e.g. at 300 DEG  to 500 DEG  F.  The phosphosulphurized product may be further treated by blowing with nitrogen, ammonia, or alcohols, at elevated temperatures such as 100 DEG  to 400 DEG  F. to remove loosely bound sulphur, or by reacting with basic reacting compounds such as metal hydroxides, amines, or guanyl compounds.  The preferred method of stabilizing the reaction product consists in reacting it with a hydrocarbon having at least one olefinic double bond, e.g. a terpene such as turpentine, dipentene, alpha-pinene, and terpinene or an olefine such as isobutylene or di-isobutylene. This further treatment is preferably carried out at from 60 DEG  to 400 DEG  F. using about 2 to 30 per cent by weight of the olefinic hydrocarbon.  In an example a Panhandle brightstock having a viscosity of 165 S.U.S. at 210 DEG  F. obtained from a Texas Panhandle mineral oil residuum and containing 2 to 3 per cent by weight of naturally occurring resins blended with 10 and 20 per cent by weight respectively of a wax-free, asphalt-free petroleum resin oil having an S.U.S. viscosity at 210 DEG  F. of 2500 and obtained by propanol precipitation from a Pennsylvania residual oil and the blend is reacted with P2S5 at 425 DEG  F., and the product filtered and then treated with dipentene for one hour at 380 DEG  F. The properties of a mineral oil lubricant containing the dipentene-treated product are compared with those of the same oil containing products obtained in the same way but using either the bright stock alone or the bright stock containing 5 per cent of a medium pine tar oil consisting mainly of phenols and terpenes as starting material for the phosphosulphurization.  Specification 687,417 is referred to.ALSO:Additives for mineral oils, which may be lubricating oils, motor or diesel fuels, hydraulic fluids, cutting oils or flushing oils are obtained by reacting a mineral oil with a phosphorus sulphide in the presence of 5 to 25 per cent by weight, based on the total hydrocarbon blend, of a waxfree and asphalt-free petroleum resin having an S.U.S. viscosity at 210 DEG F. of at least 800 and which has been solvent precipitated from a paraffinic type petroleum oil residium, whereby the sulphur content of the phosphosulphurized mineral oil is more than 6 per cent by weight (see Group IV(b).  The petroleum resin may be precipitated from the petroleum oil residium by treatment with a liquified normally gaseous hydrocarbon, e.g. propane, and should preferably have a Saybolt viscosity at 210 DEG F. of 1000 to 4000 seconds or more and a molecular weight above 1000.  The mineral oil used for the reaction should preferably have an S.U.S. viscosity at 210 DEG F. of about 450 to 300 and may be obtained from Pennsylvania crudes, or mid-Continent crudes such as Panhandle crudes.  Specified phosphorus sulphides are P2S3, P4S3, P4S7 and P2S5.  The phosphosulphurised product may be further treated by blowing with nitrogen, ammonia, or alcohols at elevated temperatures, e.g. 100 DEG  to 400 DEG F., or by reacting with basic reacting compounds such as metal hydroxides, amines or quanyl compounds.  The preferred method of establishing the reaction product consists in reacting it with a hydrocarbon having at least one olefinic double bond, e.g. a terpene such as turpentine, dipentene, alpha-pinene, and terpinene or an olefine such as isobutylene or diisobutylene.  In an example a Panhandle bright stock having a viscosity of 165 S.U.S. at 210 DEG F. obtained from a Texas Panhandle mineral oil residium and containing 2 to 3 per cent by weight of naturally occuring resins is blended with 10 and 20 per cent by weight respectively of a wax-free asphalt-free, petroleum resin oil obtained by propane precipitation of a Pennsylvania residual oil and having an S.U.S. viscosity at 210 DEG F. of 2500 and the resulting blend is reacted with P2S5 at 425 DEG F. and the product filtered and further treated with dipentene for one hour at 380 DEG F.  The properties of a mineral oil lubricant containing the dipentene-treated product are compared with those of the same oil containing products obtained in the same way but using either the bright stock alone or the bright stock containing 5 per cent of a medium pine tar oil consisting mainly of phenols and terpenes as starting material for the phosphosulphurization.  The mineral oil compositions containing the additive may also include other additives, e.g. detergency improvers, antioxidants, pour point depressants, and viscosity index improvers.  Specification 687,417 is referred to.