Patent GB-782058-A (GB)
Title: Organic metal compositions and methods of preparing same
IPC: C10M159/20
Filed: 1955-01-18
Abstract: Lubricant additives comprise high metal content, oil-soluble liquid compositions prepared by treating an anhydrous mixture of an oilsoluble organic acid or metal salt thereof, an organic hydroxy compound (as defined below) having the hydroxy group bonded to nonbenzenoid carbon, and an alkali or alkaline earth metal (including magnesium) compound (as defined below) present in substantial stoichiometric excess over the acid or salt, with a normally liquid or gaseous inorganic acid material having an ionization constant greater than 1.5 X 10-11 in water at 25 DEG  C., conditions being such that any water liberated in the reaction is substantially all driven off as it is formed.  The organic acid may be a carboxylic acid, preferably of at least 12 carbon atoms, a thiocarboxylic acid, a sulphur acid, a phosphorus acid or a thio-phosphorus acid. Specific types of organic acids include fatty acids; cyclo-aliphatic and aliphatic-substituted aromatic acids; substituted carboxylic acids such as carbamic, ricinoleic, chlorstearic and nitrolauric acids; sulphonic, sulphamic, sulphinic, sulphenic and thiosulphonic acids which may be substituted; organic phosphorous, phosphoric, phosphonic and phosphinic acids or thio analogues, particularly those of formulae: <FORM:0782058/III/1> where X and X1 are oxygen or sulphur at least one of each being sulphur, and R and R1 are each organic radicals or hydrogen at least one of each being an organic radical and at least one of each being hydrogen.  Mixtures of such acids or salts may be used, e.g. a sulphonic acid and a phosphorus acid or salt. The hydroxy compound is defined as a compound, other than a phenol, of formula Q (OH)n where Q is an acyclic or substituted cyclic organic radical having at least one non-benzenoid carbon atom to which the OH is bonded, n is an integer from 1 to 4, and said compound has an ionization constant not greater than 1X10-11 in water at 25 DEG  C.  Monohydric and polyhydric alcohols which may contain substituents, e.g. halogen atoms or amino, sulphide, disulphide or ether groups, are included.  The metal compounds are defined as basic compounds from which the metal cation is liberated when contacted with an acidic material having an ionization constant of at least 1.5 X 10-11 in water at 25 DEG  C.  Alkali and alkaline earth oxides, hydroxides, sulphides, hydrosulphides, amides and alcoholates are specified.  The inorganic acid material includes acids and acid anhydrides, e.g. hydrochloric, sulphuric, nitric and carbonic acids, HCl,SO2, SO3, CO2 (or air containing it), NO2, H2S, N2O2, PCl3, SOCl2, C102, H2Se, BF3, CS2 and COS.  The reaction temperature ranges from atmospheric or below to about 200 DEG  C. Carbon dioxide and the metal compound are preferably added portionwise to a mixture of the acid or salt and the alcohol suitably at refluxing temperature.  Alternatively, the gas is bubbled into a mixture of the other components generally in sufficient amount to neutralize them.  The amount of alcohol is usually at least 0.1 equivalent weight for each equivalent of metal compound.  The product may be treated as by distillation to remove volatiles, and filtered. Numerous examples are given, the acid material being CO2 or in one case SO2; the alkali or alkaline earth compound being BaO, LiOH.H2O, barium alcoholate (from 2-ethylhexanol or methanol) or magnesium methylate; the organic acid or salt being barium, magnesium, calcium, sodium or lead petroleum sulphonate or the free acid, barium polydodecylbenzene sulphonate, the barium salt of a thio-phosphorus acid prepared by treating polyisobutene first with P2S5 and S and then with steam, the acid prepared from polyisobutene, thiophosphoryl chloride and steam, O, O-di-n-hexyl (or isooctyl or 2-methyl pentyl-4) dithiophosphoric acid, dieicosyl salicylic acid, naphthenic acid or mixtures of these; and the hydroxy ocmpound being methanol, n- or isopropanol, n-butanol, 2-methylpentanol-4, n-hexanol, nonanol, glycerol, glycol, benzyl alcohol, cyclohexanol, furfuryl alcohol, dichlorbenzyl alcohol, monochlormethylcyclohexanol, ethyl "Cellosolve" (the word "Cellosolve" is a Registered Trade Mark) and ethanolamine.  Mineral oil is present during the reaction. Specifications 743,842 and 744,405 are referred to.ALSO:High metal content, oil-soluble liquid compositions are prepared by treating an anhydrous mixture of an oil-soluble organic acid or metal salt thereof, an organic hydroxy compound (as defined below) having the hydroxy bonded to non-benzenoid carbon, and an alkali or alkaline earth metal (including magnesium) compound (as defined below) present in substantial stoichiometric excess over the acid or salt, with a normally liquid or gaseous inorganic acid material having an ionization constant greater than 1.5 X 10-11 in water at 25 DEG  C., conditions being such that any water liberated in the reaction is substantially all driven off as it is formed.  The organic acid may be a carboxylic acid, preferably of at least 12 carbon atoms, a thiocarboxylic, a sulphur or phosphorus acid or thio analogue, including fatty acids; cycloaliphatic and aliphatic-substituted aromatic; substituted carboxylic acids such as carbamic, ricinoleic, chlorstearic and nitro-lauric; sulphonic, sulphamic, sulphinic, sulphenic and thiosulphonic which may be substituted; organic phosphorous, phosphoric, phosphonic, phosphinic or thio analogues, particularly those of formul\mg <FORM:0782058/IV (a)/1> and <FORM:0782058/IV (a)/2> where X and X1 are oxygen or sulphur, at least one of each being sulphur, and R and R1 are each organic radicals or hydrogen, at least one of each being an organic radical and at least one hydrogen.  Mixtures of such acids or salts may be used, e.g. a sulphonic acid and a phosphorus acid or salt.  The hydroxy compound is defined as a compound other than a phenol of formula Q(OH)n where Q is a (substituted) cyclic or acyclic organic radical having at least one nonbenzenoid carbon atom to which the OH is bonded, n is an integer from 1 to 4, and said compound has an ionization constant not greater than 1 X 10-11 in water at 25 DEG  C. Monohydric and polyhydric alcohols which may contain substituents, e.g. halogen, amino, sulphide, disulphide and ether, are included. The metal compounds are defined as basic compounds from which the metal cation is liberated when contacted with an acidic material having an ionization constant of at least 1.5 X 10-11 in water at 25 DEG  C.  Alkali and alkaline earth oxides, hydroxides, sulphides, hydrosulphides, amides, and alcoholates are specified.  The inorganic acid material includes acids and acid anhydrides, e.g. hydrochloric, sulphuric, nitric, and carbonic acids, HCl, SO2, SO3, CO2 (or air containing it), NO2, H2S, N2O2, PCl3 SOCl2, ClO2, H2Se, BF3, CS2, and COS.  The reaction temperature ranges from atmospheric or below to about 200 DEG  C.  Carbon dioxide and the metal compound are preferably added portionwise to a mixture of the acid or salt and the alcohol suitably at refluxing temperature.  Alternatively the gas is bubbled into a mixture of the other components generally in sufficient amount to neutralize them.  The amount of alcohol is usually at least 0.1 equivalent weight for each equivalent of metal compound.  The product may be treated as by distillation to remove volatiles, and filtered.  Numerous examples are given, the acid material being CO2 or in one case SO2; the alkali or alkaline earth compound being BaO, LiOH.H2O, barium alcoholate (from 2-ethylhexanol or methanol) or magnesium methylate; the organic acid or salt being barium, magnesium, calcium, sodium or lead petroleum sulphonate or the free acid, barium polydodecylbenzene sulphonate, the barium salt of a P-S-acid prepared by treating polyisobutene with P2S5 and S, then with steam, the acid prepared from polyisobutene, thiophosphoryl chloride and steam, o,o-di-n-hexyl (or iso-octyl or 2-methyl pentyl-4) dithiophosphoric acid, dieicosyl salicylic acid, naphthenic acid, or mixtures of these; and the hydroxy compound being methanol, n- or iso-propanol, n-butanol, 2-methylpentanol-4, n-hexanol, nonanol, glycerol, glycol, benzyl alcohol, cyclohexanol, furfuryl alcohol, dichlorbenzyl alcohol, monochlormethylcyclohexanol, ethyl "Cellosolve" (Registered Trade Mark), and ethanolamine.  Mineral oil is present during the reaction.  The products are lubricant additives, paint driers, stabilizers for plastics, emulsifiers, fat-splitting agents, and rust-preventatives.  Specifications 743,842 and 744,405 are referred to.