Patent GB-1009913-A (GB)
Title: Phosphorus- and nitrogen-containing compositions and lubricating compositions containing them
IPC: C07F9/165
Filed: 1962-07-13
Abstract: A lubricating composition comprises a major proportion by weight of a lubricating oil and a minor proportion by weight of a phosphorus-and nitrogen containing composition obtained by forming an acidic intermediate by reacting a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide or phosphorus halide and neutralizing a substantial proportion (generally at least 50%) of said acidic intermediate with an amine (see Division C2).  The hydroxy-substituted ester is suitably one having the formula (RO)2P(X)XR wherein R is selected from hydrocarbon and hydroxy-substituted hydrocarbon radicals which hydrocarbon radicals may be unsubstituted or may contain no more than one polar group, e.g. Cl, Br, I, alkoxy, aryloxy, nitro, keto or aldehyde, and X is oxygen or sulphur, at least one X being sulphur and at least one R group being a hydroxy-substituted hydrocarbon radical and preferably an hydroxyalkyl group of up to 8 C-atoms. The inorganic phosphorus compound is preferably P2O5 and the preferred amine for the neutralization step is a tertiary alkyl primary amine having 12 or more carbon atoms.  The lubricating oil may be a synthetic, animal, vegetable or mineral oil and is preferably a mineral oil or a synthetic polyester oil. Other conventional additives may also be present especially aliphatic (including aralkyl), cycloaliphatic and aromatic (including alkaryl),di-, tri- and poly-sulphides; salts of petroleum napthenic acids, petroleum sulphonic acids, or of oil-soluble fatty acids; a neutralization product of triethylene tetramine with a C50 alkenyl substituted succinic anhydride; a copolymer of 5 parts betadiethyl-aminoethyl acrylate with 95 parts of dodecyl methacrylate, and oxidation inhibitors, film strength agents, oiliness agents, pour point depressors, foam inhibitors, and viscosity index improvers of known type. Several specific mineral oil compositions containing the defined additives are exemplified.ALSO:A phosphorus- and nitrogen-containing composition is obtained by reacting a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide, or phosphorus halide and neutralizing a substantial portion (generally at least 50%) of the acidic intermediate formed with an amine.  The hydroxy-substituted ester is preferably of the type (R11O)2.P(S).S.R1OH wherein R11 is a hydrocarbon radical, e.g. a polyisobutene radical (molecular weight 1500) polyisobutene (molecular weight 350) substituted phenyl radical and R1 is a bivalent hydrocarbon group, e.g. an alkylene or arylene group which may be substituted by not more than one polar group, e.g. Cl, Br, I, alkoxy, aryloxy, nitro, keto or aldehyde group.  The inorganic phosphorus compound is preferably P2O5 and the amine used may be aliphatic, cycloaliphatic, aromatic or heterocyclic and is preferably a tertiary alkyl primary amine containing 12 or more carbon atoms. The products are useful as insecticides and rust-preventing agents and as lubricant additives (see Division C5).ALSO:A phosphorus- and nitrogen-containing composition is obtained by forming an acidic intermediate by reacting a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide or phosphorus halide and neutralizing a substantial portion of the acidic intermediate with an amine. The hydroxy-substituted esters are suitably those having the formula (RO)2P(X)XR, wherein R is selected from hydrocarbon- and hydroxy - substituted - hydrocarbon radicals which hydrocarbon radicals may contain no more than one polar group, at least one R being a hydroxy-substituted hydrocarbon radical as defined above and X is oxygen or sulphur, at least one X being sulphur.  The hydrocarbon radicals may be aromatic, aliphatic or cycloaliphatic and may contain no more than one polar group, e.g. Cl, Br, I, alkoxy, aryloxy, nitro, keto or aldehydo. Specified hydrocarbon groups include alkyl and cycloalkyl groups, the polyisobutene radical (M.W. 1500), aryl, aralkyl and alkaryl groups including the polypropylene (M.W. 300) substituted phenyl group and preferred hydroxy-substituted hydrocarbon groups are those having less than 8 carbon atoms, e.g. hydroxy-ethyl, -propyl, -butyl or -octyl and 3 - chloro - hydroxy - propyl.  The inorganic phosphorus compound may be phosphorus-pentoxide, -trioxide or -tetroxide, phosphoric, pyrophosphoric, metaphosphoric, or hypophosphoric acid, phosphorous, metaphosphorous or hypophosphorous acid, PCl3, PBr3, PI3, PCl5, PBrCl4, POCl3 or PSCl3.  The reaction to form the acidic product is preferably effected at elevated temperature, e.g. above 50 DEG  C. but usually below 150 DEG  C. and from 1 to 5 moles of the triester is generally used for each mole of the inorganic phosphorus compound. The amine used in the neutralization step may be an aliphatic, aromatic, cyclo-aliphatic or heterocyclic amine and is preferably a tertiary alkyl primary amine having 12 or more C atoms. The neutralization may be carried out at from 0 DEG  to 200 DEG  C. and the product is mainly a salt when the reaction temperature is below 80 DEG  C. although at temperatures above 100 DEG  C. it may contain amides or amidines or mixtures thereof. Generally sufficient amine should be used to neutralize at least 50% of the intermediate acidic product.  Several examples are given and the products are useful as insecticides (see Division A5), as rust-preventing agents and a additives for lubricants (see Division C5).  Suitable hydroxy-substituted thiophosphate esters for use as starting materials are obtained by reacting a dithiophosphate with an epoxide, a glycol or an unsaturated alcohol, e.g. alkyl, cinnamyl or oleyl alcohol.ALSO:An insecticidal composition contains as active ingredient a phosphorus and nitrogen-containing product obtained by reacting a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide or phosphorus halide and neutralising a substantial portion (generally at least 50 per cent) of the resulting acidic intermediate with an amine (see Division C2).  The hydroxy-substituted triester is preferably one having the formula (R110)2.P(S).  SR1OH wherein R11 is a hydrocarbon radical which may be substituted by no more than one polar group, e.g. Cl, Br, I, alkoxy, aryloxy, nitro, keto or aldehydo and R1 is a sivalent hydrocarbon radical, e.g. alkylene or arylene, which may be substituted as defined for R11 above.  The radicals R11 may be aromatic, aliphatic or cycloaliphatic and the amine used may be an aliphatic, cycloaliphatic, aromatic or heterocyclic amine, the preferred amine being a tertiary alkyl primary amine having 12 or more carbon atoms.  The composition may be in the form of an emulsion e.g. an emulsion made from water, sodium dodecyl benzene sulphonate and a kerosene solution containing the product obtained by reacting hydroxypropyl 0, 01-bis (di-chlorophenyl) phosphorodithisate with P2O5 and then treating with a tertiary aliphatic primary amine mixture having an average molecular weight of 315.