Patent GB-705273-A (GB)
Title: Lubricating compositions
IPC: C10M159/12
Filed: 1951-02-02
Abstract: Condensation products are prepared by reacting an alkylene oxide, sulphide or imine or a substitution product thereof with a polyacidic organic compound containing either at least one group -XR and at least two groups -COXR, or at least one group -XR, a group -COXR and an inorganic oxy-acid group, the symbol X representing an oxygen or sulphur atom and R representing a hydrogen atom, an alkyl, cycloalkyl, aralkyl, alkaryl or aryl group or a metal atom or organic base radical, at least one of the Rs being a hydrogen atom.  The polyacidic organic compound may be aliphatic, aromatic or heterocyclic; the inorganic oxy-acid group may be a sulphonic acid, sulphinic acid, oxy acid of phosphorus or nitro group and the acid group may be in the form of a salt of Na, Li, K, Ca, Ba, Sr, Sn, Ni, Al, Zn, Pb or an organic amine; they may contain additional substituents such as nitro, nitroso, amino or sulphonic acid groups or halogen atoms.  Examples include hydroxy malonic, hydroxy succinic, octyl tartaric, citric, hydroxy glutaric, hydroxy adipic, chlormalic, mercapto succinic, chloro hydroxy-succinic, hydroxy phthalic, mercapto phthalic, sulpho hydroxy phthalic, hydroxy dithiosebacic, hydroxy phenylene dithio dicarboxylic, S-phenyl thiomalic, naphthol dicarboxylic, 2-propyl-4-hydroxy thiophene-3:4-dicarboxylic, thio tartaric and di-thio tartaric acids, and naphthol-3-carboxylic-6-sulphonic acid; partial or neutral esters of these acids including acid oleyl, stearyl or cetyl esters of citric acid, diphenyl tartrates, and trioleyl citrate; salts of such acids or acid esters, e.g. sodium salt of the acid oleyl ester of malic acid, the triethanolamine salt of the acid stearyl ester of citric acid and the dibutylamine salt of the acid oleyl ester of tartaric acid. These compounds may be reacted with, e.g. 1 to 30 moles. of ethylene, propylene, butylene or amylene oxide, epichlorhydrin, glycide, alkyl substituted glycides, glycidyl iso-propyl ether and ethylene or propylene sulphide or imine. Temperatures of 50-350 DEG C. and pressures of up to 1,000 lbs. or more may be used. Condensation catalysts including boric acid, caustic alkalies, alkali alcoholates, sodium oleate, di-sodium phosphate, sodium di-hydrogen phosphate and organic amines, e.g. ethylene diamine and diluents such as benzene, kerosine, gas oil, mineral oil, dioxane or liquid alkylated naphthalene may be present. The condensation products may be halogenated, sulphurized, p halo-sulphurized, phosphorized or sulpho-phosphorized with e.g. chlorine, sulphur, sulphur chloride, sodium polysulphide, phosphorus, phosphorus sulphides and phosphorus oxychloride.  The condensation products are additives for lubricating oils including mineral, vegetable and animal oils, polymerised olefines, esters and silicone polymers such as dimethyl silicone polymer and may be used in conjunction with the usual lubricant additives, many of which are specified (see Group III).  Condensation products described are prepared from ethylene oxide and tartaric acid, malic acid, methylene di-salicylic acid, acid oleyl ester of malic acid, octyl mercapto acid phthalate, di-oleyl malate and b -sulphonic acid or o -hydroxy decyl carboxylic acid respectively; propylene oxide and hydroxy glutamic acid; ethylene sulphide and tartaric acid, malic acid, dioleyl malate and the mono-butyl ester of a , a 1-bis (12-hydroxy stearic acid) disulphide respectively; amylene oxide and dibenzyl tartrate; glycidyl isopropyl ether and dioleyl malate; ethylene imine and dioleyl malate; the ethylene oxide-dioleyl malate condensate is sulphurized by reaction with sulphur or phospho-sulphurized with P2S5.  Lubricating compositions comprising some of these condensates are described.ALSO:Condensation products are prepared by reacting an alkylene oxide, sulphide or imine or a substitution product thereof with a polyacidic organic compound containing either at least one group -XR and at least two groups -COXR, or at least one group -XR, a group -COXR and inorganic oxyacid group, the symbol X representing an oxygen or sulphur atom and R representing a hydrogen atom, an alkyl, cycloalkyl, aralkyl, alkaryl or aryl group or a metal atom or organic base radical, at least one of the Rs being a hydrogen atom.  The polyacidic organic compounds may be aliphatic, aromatic or heterocyclic; the inorganic oxy-acid group may be a  sulphonic acid, sulphinic acid, oxyacid of phosphorus or nitro group and the acid group may be in the form of a salt of Na, K, Li, Ca, Ba, Sr, Sn, Ni, Al, Zn, Pb or an organic amine; they may contain additional substituents such as nitro, nitroso, amino or sulphonic acid groups or halogen atoms.  Examples include hydroxy malonic, hydroxy succinic, octyl tartaric, citric, hydroxy glutaric, hydroxy adipic, chlormalic, mercapto succinic, chloro hydroxy succinic, hydroxy phthalic, mercapto phthalic, sulpho hydroxy phthalic, methylene disalicylic, hydroxy dithiosebacic, hydroxy phenylene dithio dicarboxylic, S-phenylthiomalic, a , a 1-bis (12-hydroxy stearic) disulphide, naphthol dicarboxylic, 2-propyl-4-hydroxy-thiophane-3:4-dicarboxylic, thio-tartaric and dithio tartaric acids, b -sulphonic acid of o -hydroxy decyl or octyl carboxylic acid and naphthol-3-carboxylic-6-sulphonic acid; partial or neutral esters of these acids including, e.g. acid oleyl, stearyl or cetyl esters of citric acid, diphenyl tartrate and trioleyl citrate; salts of such acids or acid esters including, e.g. sodium salt of the acid oleyl ester of malic acid, triethanolamine salt of the acid stearyl ester of citric acid and dibutylamine salt of the acid oleyl ester of tartaric acid.  These compounds may be reacted with, e.g. 1 to 30 moles. of ethylene, propylene, butylene or amylene oxide, epichlorhydrin, glycide, alkyl-substituted glycides, glycidyl iso-propyl ether and ethylene or propylene sulphide or imine. Reaction may be effected at about 50 DEG -350 DEG C. at pressures up to 1,000 lbs. or more.  Condensation catalysts such as boric acid, caustic alkalies, alkali alcoholates, sodium oleate, disodium phosphate, sodium dihydrogen phosphate and organic amines, e.g. ethylene diamine and diluents such as benzene, kerosene, gas oil, mineral oil, dioxane or liquid alkylated naphthalene may be present. The condensation products may be halogenated, sulphurized, halosulphurized, phosphorized or sulpho-phosphorised with, e.g. chlorine, sulphur, sulphur chloride, sodium polysulphide, phosphorus, phosphorus sulphides, phosphorus oxides and phosphorus oxychloride. Any free acid groups in the condensation products may be neutralized with metallic or organic bases.  The condensation products are used as additives to lubricating oils (see Group III).  Examples describe the preparation of condensation products from ethylene oxide and tartaric acid, malic acid, methylene disalicylic acid, the acid oleyl ester of malic acid, octyl mercapto acid phthalate, di-oleyl malate and b -sulphonic acid of o -hydroxy decyl carboxylic acid respectively; propylene oxide and hydroxy glutamic acid; ethylene sulphide and tartaric acid, malic acid, dioleyl malate and the mono-butyl ester of a , a 1-bis (12-hydroxystearic acid) disulphide respectively; amylene oxide and dibenzyl tartrate; glycidyl isopropyl ether and dioleyl malate; ethylene imine and dioleyl malate; the ethylene oxide-dioleyl malate condensate is sulphurized by reaction with sulphur or phosphosulphurized with phosphorus pentasulphide.ALSO:Lubricating compositions comprise an organic lubricant and, as stabilizer and extreme pressure additive, a minor proportion of a condensation product prepared by reacting an alkylene oxide, sulphide or imine or a substitution product thereof with a poly acidic organic compound containing at least one group -XR and at least two groups-COXR or containing at least one group-XR, a group-COXR and an inorganic oxyacid group, wherein X is oxygen or sulphur and R is a hydrogen atom, an alkyl, cycloalkyl, aralkyl, alkaryl or aryl group or a metal atom or organic base radical, at least one R being hydrogen (see Group IV (b)).  The poly acidic compounds may be aliphatic, aromatic or heterocyclic; the oxy acid group may be a sulphonic acid, sulphinic acid, oxy acid of phosphorus or a nitro group and may be in the form of a salt of Na, K, Li, Ca, Ba, Sr, Sn, Ni, Al, Pb, Zn or an organic amine; they may contain additional substituents, e.g. nitroso or amino groups or halogens. Examples of these include hydroxy malonic, hydroxy succinic, octyl tartaric, citric, hydroxy glutaric, hydroxy adipic, chlormalic, mercapto succinic, chloro-hydroxy succinic, hydroxy phthalic, mercapto phthalic, sulpho hydroxy phthalic, hydroxy dithiosebacic, hydroxy phenylene dithio dicarboxylic-, S-phenyl thio malic, naphthol dicarboxylic-, 2-propyl-4-hydroxy thio phane-3: 4- dicarboxylic-, thio tartaric and di-thio tartaric acids; partial or neutral esters of these acids including acid stearyl citrate, diphenyl tartrate and trioleyl citrate; salts of such acids and acid esters, e.g. sodium acid oleyl malate, triethanolamine acid stearyl citrate and dibutylamine acid oleyl tartrate.  These poly acidic compounds are condensed with 1 to 30 mols of ethylene, propylene, butylene, or amylene oxide, epichlorhydrin, glycide, alkyl substituted glycides or other glycidyl compounds and analogous sulphides or imines.  The products may be further treated with, e.g. sulphur, chlorine, sulphur chloride, sodium polysulphide, phosphorus, phosphorus sulphides, phosphorus oxides or phosphorus oxychloride. The organic lubricant may be a natural or synthetic oil such as a mineral, vegetable, animal or marine oil, polymerized olefine, an ester, e.g. di-octyl phthalate, di(2-ethyl hexyl) sebacate or trioctyl phosphate or a silicone polymer, e.g. dimethyl silicone polymer.  There may also be present secondary additives such as the poly acidic compou