Patent GB-676777-A (GB)
Title: Improvements in or relating to lubricating oil compositions
IPC: C10M137/10
Filed: 1949-03-17
Abstract: Dithiophosphoric acid triesters of formul  <FORM:0676777/IV (b)/1> and <FORM:0676777/IV (b)/2> where X is O or S, each R is an aliphatic or aromatic hydrocarbon radicle, R1 is an aliphatic hydrocarbon radicle, R2 is hydrogen or an aliphatic hydrocarbon radicle and n is an integer greater than 1, are made by the processes of Specification 676,776, which is referred to, c.f. Group IV (b), which also contains all the present specified starting materials and products together with the necessary conditions of the reaction.  In the Specification as open to inspection under Sect. 91, R1 may be an aromatic radicle, the derivatives then being made by reacting an O,O-disubstituted dithiophosphoric acid with a vinyl aryl ether.  Many of these ethers are specified.  This subject-matter does not appear in the Specification as accepted.ALSO:Lubricating oil compositions comprise a hydrocarbon oil with a dithiophosphoric acid triester of formula <FORM:0676777/III/1> where R is an aliphatic or aromatic hydrocarbon radicle, R1 is an aliphatic hydrocarbon radicle, R2 is hydrogen or an aliphatic radicle, X is O or S and n is a whole number greater than 1.  The esters are preferably present in amounts of about 0.1 to 5 per cent, quantities of 0.2 to 3 per cent usually being added to automobile engine oils.  They are compatible with common additives such as detergents, stabilizers, sludge-inhibitors, aliphatic or aromatic sulphonates, e.g. calcium petronate, and alkyl phenol sulphides, e.g. p, p1-dibutyl-, diamyl- or dioctyl-phenol mono- or poly-sulphides and 2, 4-dialkyl phenol mono- or poly-sulphides and their metal salts.  These other additives are usually present to the extent of about 0.1-5 per cent, e.g. about 0.5-2 per cent.  At relatively low temperatures derivatives of O, O-dialkyl-dithio-phosphoric acids containing lower alkyl groups, e.g. methyl, ethyl, propyl or butyl radicles, are preferred.  A large number of O, O-disubstituted dithiophosphoric acids, mono- and polyhydric alcohols, mono- and polymercaptans, vinylethers and vinylthioethers are specified for the production of the esters according to the process of Specification 676,776, [Group IV(b)].  In examples the following esters are made and added to hydrocarbon oils; (1) diethyl- and diphenyl-S-ethoxymethyl-; (2) di-n-propyl-S-isopropoxymethyl- and diisopropyl-S-ethoxymethyl-; (3) di-n-butyl-S-ethoxymethyl-; (4) di-isobutyl-S-methyoxymethyl- and (5) di-methylisobutylcarbinyl - S - methoxymethyl-dithiophosphate; (6) a dithiophosphoric acid diester made by reacting a mixture of B 24 alcohol of U.S.A. Specification 2,368,000, n-decanol, p-octylphenol and methylisobutyl carbinol with P2S5 and reacting the product with methanol and formaldehyde; (7) and (8) the esters made by reacting diethyl-dithiophosphoric acid and formaldehyde with nopol (a Methylolpinene produced by reacting formaldehyde with Ceta-pinene), hydronopol or tert butyl mercaptan; (9) di-n-propl- and di-isobutyl-S-t-butylthiomethyl-; (10) diethyl-S-amylthiomethyl- and (11) diethyl-S-n-octylthiomethyldithiophosphate; (1) O, O-di-n-butyldithiophosphatemethylmercaptoethanol; (13) O, S-bis (O, O-di-n-butyldithiophosphatemethyl) mercaptoethanol; (14) O, O-diethyldithiophosphatoethyl n-butyl ether; (15) O, O-diethyldithiophosphatoethyl isobutyl ether; (16) O, O-dibutyldithiophosphatoethyl n-butyl ether; (17) O, O-dicyclohexyl dithiophosphatoethyl n-butyl ether; (18) O, O-diethyldithiophosphatoethyl 2-ethyl hexyl ether; (19) the reaction product of the dithiophosphoric acid diester of (6) with vinyl n-butyl ether; (20) O, O-di-n-propyl-S-ethoxyethylidene-; (21) O, O-di-n-propyl-S-ethoxybutylidene- and (22) O, O-diethyl-S-tert. butylthioethylidene-dithiophosphate; and (23) the reaction product of diethyldithiophosphoric acid with ethanol and heptaldehyde. Specification 567,939 also is referred to.  The Specification as open to inspection under Sect. 91, refers to R1 in the general formula as representing an aromatic radicle when the derivatives are made by reacting an O, O-disubstituted dithiophosphoric acid with a vinyl aryl ether. Many of these ethers are specified.  This subject-matter does not appear in the Specification as accepted.