Patent GB-862578-A (GB)
Title: Catalytic phosphosulfurization of hydrocarbons
IPC: C07F9/04
Filed: 1959-04-02
Abstract: In a process in which phosphorus pentasulphide is reacted with a hydrocarbon material at a temperature in the range of 350 DEG  to 600 DEG  F. to obtain a product useful as a lubricant additive containing at least 2% weight of combined phosphorus and at least 4% weight of combined sulphur, the reaction rate is increased and a clearer product is obtained by having present in the reaction mixture as catalyst an amount of from 0.01 to 0.1% weight based on the total reaction mixture of an oxygen acid of phosphorus.  The hydrocarbon material may be a paraffin wax or petroleum bright stock (see Group IV (b)) or a C2 to C20 mono-olefin polymer having a molecular weight of 500 to 100,000, e.g. polyethylene, polypropylene, polyisobutylene, or a copolymer of a mono-olefin with other olefins, e.g. with isoprene or styrene. Suitable oxygen acids of phosphorus are HPO3, H3PO4 and H3P2O6.P2O5 may also be used provided sufficient water is present to convert it to the required amount of oxygen acid of phosphorus.  The catalyst can be added directly to the reaction mixture or may be premixed with the P2S5.  Also, the catalyst need not be present initially, but may be added subsequently in the early stages of the reaction when the mixture is at a temperature above 300 DEG  F.  The reaction is preferably carried out under a blanket of nitrogen, carbon monoxide, inert refinery gas, or fuel gas and the free oxygen content should not exceed about 0.1% weight and the free water content should not exceed 0.5% weight.  The reaction product may be further treated by stripping, extraction or dilution or by reacting with a neutralizing agent.  Thus, polyisobutylene phosphosulphurized by the process may be reacted at 300 DEG  F. with a high alkalinity barium sulphonate to yield a detergent oil additive.  Examples are given for the phosphosulphurization of polyisobutylene (average molecular weight above 1100 (Staudinger)) in the presence of HPO3, P2O5 (in the presence of water) and H3PO4. A comparative example is also given in which the phosphosulphurization is carried out in the presence of P4S4O6 which is shown to have a deleterious effect on the reaction.  Specification 693,422 is referred to.ALSO:In a process in which phosphorus pentasulphide is reacted with a hydrocarbon material at a temperature in the range of 350 DEG  to 600 DEG  F. to obtain a product useful as a lubricant additive containing at least 2% by weight of combined phosphorus and at least 4% by weight of combined sulphur the reaction rate is increased and the obtainance of a clear product free of sediment is enhanced by having present in the reaction mixture as catalyst an amount of from 0,01 to 0,1 weight per cent. based on the total reaction mixture of an oxygen acid of phosphorus.  The hydrocarbon material may be a paraffin wax, a petroleum bright stock or a C2 to C10 monoolefin polymer or copolymer (see Group IV(a)).  Suitable bright stocks are those obtained by topping crude oils and extracting or deasphaltting the residues or those obtained by catalytic cracking of cycle stocks.  Suitable oxygen acids of phosphorus are HPO3, H3PO4 and H3P2O6. P2O5 may also be used provided there is present sufficient water to convert it to the required amount of oxygen acid of phosphorus.  The oxygen-acid of phosphorus can be added directly to the reaction mixture or may be pre-mixed with the P2S5.  Also, the catalyst need not be present initially but may be added subsequently in the early stages of the reaction when the mixture is at a temperature above 300 DEG F.  The reaction is preferably carried out under a blanket of nitrogen, carbon monoxide, inert refinery gas, or fuel gas and the free oxygen content should not exceed about 0,1 weight per cent. and the water content should not exceed 0,5 weight per cent. The reaction product can be further treated, e.g. by stripping, extraction or dilution or by reacting with a neutralising agent. Specification 693,422 is referred to.