Patent GB-682442-A (GB)
Title: Improvements in stabilized hydrocarbon compositions
IPC: C10L1/30
Filed: 1948-02-05
Abstract: Oil-soluble phosphorus-containing compounds are prepared by reacting an organic hydroxy acid or ester thereof with a phosphorus and halogen containing compound in which the phosphorus is in trivalent form.  The reaction products may contain also compounds resulting from replacement of the hydroxyl group of the organic hydroxyl reagent by, for example, chlorine.  The products may be halogenated and/or treated with a base, e.g. an alkali, metal or organic base to form salts or ester-salts; they may also be hydrolysed to replace by hydroxyl any halogen present that is directly linked to phosphorus. Suitable trivalent phosphorus and halogen-containing reactants are phosphorus tri-chloride, bromide and iodide and halogen derivatives of organic phosphines such as those of the classes RPCl2, RR1PCl, ROPCl2 and (RO) (R1O) PCl, wherein R and R1 are hydrocarbon radicals, e.g. phenyl, alkylated phenyl, cyclohexyl phenyl, lauryl, cetyl, cyclopentyl and cyclohexyl, such as phosphenyl chloride; suitable hydroxyacid esters include those of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, trimethylene glycol, cyclohexanol, benzyl alcohol and furfuryl alcohol with such hydroxy acids as glycollic, lactic, hydroacrylic, hydroxybutyric, glyceric, dihydroxy palmitic, tartronic, malic, citramalic, citric, tartaric and trihydroxy glutaric acids.  The phospho-halogen reactant may be reacted with mixtures of the hydroxy acids and/or the esters thereof; if desired, it may be partly reacted with one or two moles. of one hydroxy compound and the reaction completed with a different hydroxy compound.  The oil-soluble phosphorus-containing products may be converted into the salts or ester-salts by partial or complete saponification with aqueous solutions of sodium, potassium, ammonium or quaternary ammonium hydroxides or with amines; other metal salts may be obtained similarly or by decomposition with the alkali salts or ester-salts.  Certain of the oil-soluble products have the following general formul : (OH)2P-OR1COOR2 <FORM:0682442/IV (b)/1> and <FORM:0682442/IV (b)/2> wherein R1, R3 and R5 are hydrocarbon radicals and R2, R4 and R6 are hydrogen, hydrocarbon radicals, metals or metallic radicals, e.g. sodium carboxyl-propyl; esters of the type 1 (a) and 1 (b) are prepared by reacting PCl3 with appropriate proportions of hydroxyester, e.g. methyl lactate and hydrolysing with water to replace by hydroxyl, chlorine directly linked to phosphorus. p  <FORM:0682442/IV (b)/3> and <FORM:0682442/IV (b)/4> wherein R1, R3, R5 and R6 are hydrocarbon radicals and R2 and R4 are as defined above, esters of these types being obtained by reacting the selected hydroxy ester reactant with either a compound <FORM:0682442/IV (b)/5> or R5-PCl2 in appropriate proportions. <FORM:0682442/IV (b)/6> and <FORM:0682442/IV (b)/7> and such compounds may be obtained by reacting in appropriate proportions the selected hydroxy compound with a compound of the general formula <FORM:0682442/IV (b)/8> or R5-OPCl2, the Rs being as defined above. The products may be used in lubricants and fuels (see Group III). In examples: (1) PCl3 is added slowly to methyl lactate at below 60 DEG  C., the mixture being subsequently heated at 120 DEG  C. for 3 hours, yielding phosphoric esters such as P(OC2H4COOCH3)3 and P.Cl(OC2H4 COOCH3)2, and some methyl chlorpropionate which may be stripped off by distillation; (2) dibutyl tartrate, and (3) trimethyl citrate are similarly reacted. The Specification as open to inspection under Sect. 91 relates to the production of phosphorus containing compounds by reacting organic hydroxy acids or hydroxy esters, including esters of hydroxy acids and partial esters of polyhydric alcohols with organic acids, with a phosphorus-containing reagent such as P4O6, P2O4, P2O5, POCl3, POCl, POBr3 P2O3Cl4, POF3, PCl5, PF5, P2Cl4, P2S5, P4S6, P4S3, P3S6, P4S7, PSCl3, PSCl, PSBr3, P2S3Br4, P4S4O6, P2Se5, P2Se3, PS(NH)3, P(CNS)3 and PO(NH)2)3.  Many additional examples of hydroxy reagents are also given.  Reference is made to the formation of oil-soluble products of the above-given general formul  wherein the R's may be any organic radicals.  This subject-matter does not appear in the Specification as accepted.ALSO:Liquid hydrocarbon compositions for use as lubricants and fuels comprise a major proportion by weight of liquid hydrocarbons and a minor proportion of an oil-soluble phosphorus containing product resulting from the reaction of an organic hydroxy acid or ester thereof with a phosphorus and halogen containing compound in which the phosphorus is trivalent, or derivatives of such products obtained by their halogenation and/or conversion into salts or ester-salts by treatment with a base such as an alkali, metal or organic base, e.g. an amine and those obtained by hydrolyzing the oil-soluble products to replace by hydroxyl, halogen directly linked to phosphorus when present.  The liquid hydrocarbons are essentially derived from petroleum and include mineral lubricating oils, lighter fractions used as fuels and gasolines as well as hydrogenated oils and volatolized oils.  The additives serve as stabilizers against oxidation, polymerization and other deterioration; they also function as extreme pressure agents.  The compositions may be used in engines of the ignition and Diesel types.  The additives may be used in amounts of 0.001 to 0.2 per cent but also in amounts up to the limit of their solubility in, e.g. a heavy liquid hydrocarbon to form concentrates for subsequent dilution in, e.g. a lighter hydrocarbon such as gasoline or diesel fuel.  A mutual solvent may be added to facilitate solution of the additive.  The liquid hydrocarbon compositions may also include corrosion inhibitors, e.g. alkyl and aryl phosphites, extreme pressure agents of the halogen, phosphorus and/or sulphur containing types, fuel dopes, antioxidants and anti-knock compounds such as tetra-ethyl lead and iron carbonyl.  The production of the oil-soluble phosphorus containing additives is described (see Group IV(b)).  Certain of these compounds have the general formulae (OH)2 P-OR1COOR2, wherein R1, R3 and R5 are hydrocarbon radicals and R2, R4 and R6 are hydrogen, hydrocarbon radicals, metals or metallic <FORM:0682442/III/1> and <FORM:0682442/III/2> radicals, <FORM:0682442/III/3> , <FORM:0682442/III/4> and <FORM:0682442/III/5> wherein R1, R3, R5 and R6 are hydrocarbon radicals and R2 and R4 are as defined above. Examples describe the production of the oil-soluble derivatives obtained by reacting PCL3 with (1) methyl lactate yielding phosphoric esters such as P(OC2H4COOCH3)3 and PCl-(OC2H4COOCH3)3 and some methyl chlorpropionate which may be stripped off by distillation (2), dibutyl tartrate and (3) trimethyl citrate.  Many other reactants are mentioned.  The Specification as open to inspection under Sect. 91, describes the similar use in petroleum, animal, vegetable and mineral oils of the oil-soluble products obtained by reacting any phosphorus containing reagent with an organic hydroxy acid or hydroxy ester including esters of hydroxyacids and partial esters of polyhydric alcohols, or the above mentioned derivatives of the oil-soluble products.  Further examples of the hydroxy reactants are given and specified phospho-reactants include P4O6, P2O4, P2O5, POCl3, POCl, POBr3, P2O3Cl4, POF3, PCl5, PF5, P2Cl4, P2S5, P4S6, P4S3, P3S6, P4S7, PSCl3, PSCl, PSBr3, P2S3Br4, P4S4O6, P2Se5, P2Se3, PS(NH)3, P(CNS)3 and PO(NH2)3.  Reference is made to oil-soluble additives of the above given general formulae wherein the Rs may be any organic radicals.  This subject-matter does not appear in the Specification as accepted.