Patent GB-944218-A (GB)
Title: Double carbonated double basic barium sulfonates and lubricating oil compositions containing the same
IPC: C10M159/24
Filed: 1959-12-21
Abstract: Carbonated basic barium sulphonates are prepared by reacting a neutral barium sulphonate of the formula (R SO3)2 Ba or [(R)aASO3]2 Ba wherein R is a cyclic straight or branched chain, saturated or unsaturated hydrocarbon radical having a molecular weight from 150 to 800, A is an aromatic radical and a is an integer from 1 to 4, with 1 to 1.5 mols of barium hydroxide per mol of neutral barium sulphonate, reacting the resulting basic barium sulphonate with from 0.5 to 1.0 mol of CO2 per mol of excess barium contained in the basic sulphonate, then reacting the product with from 1 to 1.5 moles of barium hydroxide per mol of original neutral sulphonate and finally reacting with 0.5 to 1 mol of CO2 per mol of additional barium incorporated in the basic sulphonate.  Suitable sulphonic acids include those wherein R represents a dodecyl hexadecyl, eicosyl or triacontyl radical or a radical derived from a petroleum hydrocarbon, wax or olefine polymer; A may be a radical derived from benzene, naphthalene, anthracene or biphenyl.  Reference is made to mahogany acids and white oil alkylated benzene, di-poly propylene alkylated benzene and triacontyl sulphonic acids.  The carbonation steps may be effected, suitably at 250 DEG -400 DEG F., with CO2 gas or with urea which on heating to a sufficient temperature decomposes in situ to form CO2 and ammonia. In the examples, a lubricating oil solution of a basic barium petroleum sulphonate prepared from the neutral salt and Ba(OH)2 is (IV), treated with excess CO2 at 300 DEG F. and the carbonated product is either, V, heated with an aqueous solution of Ba(OH)2 urea at a temperature rising from 210 DEG  to 280 DEG F. to yield a double carbonated double basic barium sulphonate or VI, is reacted with aqueous Ba(OH)2 at 220 DEG F., dried and then treated with CO2 at 300 DEG F.  In addition, experiments are described wherein (1) a lubricating oil solution of a neutral barium petroleum sulphonate is obtained by repeatedly washing the oil solution of the corresponding neutral calcium salt with aqueous BaCl2; (2) an oil solution of a basic barium sulphonate is obtained from the product of (1) by reaction with aqueous Ba(OH)2 and (3) the product of (2) is carbonated with CO2. Specifications 743,842, 744,405 and 790,471 are referred to.ALSO:Lubricating oil compositions comprise a polyoxy alkylene type base oil and from 0.5 to 25% by weight of a double carbonated double basic barium sulphonate prepared by reacting a neutral barium sulphonate of the formula (RSO3)2Ba or [(R)a ASO3]2Ba, wherein R is cyclic or straight or branched chain, saturated or unsaturated hydrocarbon radical having a molecular weight of 150 to 800, A is an aromatic radical and a is an integer from 1 to 4, with 1 to 1.5 moles of barium hydroxide per mole of neutral sulphonate, reacting the resulting basic sulphonate with 0.5 to 1.0 mole of CO2 per mole of excess barium contained in the basic salt, then reacting the carbonated product with 1 to 1.5 moles of barium hydroxide per mole of original neutral sulphonate and finally reacting the double basic sulphonate with 0.5 to 1 mole of CO2 per mole of additional barium incorporated in the basic sulphonate (see Division C2). The base oil may be an alkylene oxide polymer, an ester of an ethylene oxide polymer, a polymer of an alkylene oxide with water or an alcohol or a polyether prepared from an ethylene oxide. Specifications 743,842, 744,405 and 790,471 are referred to.ALSO:Lubricating compositions comprise a lubricating oil and from 0.5 to 25% by weight of a double carbonated double basic barium sulphonate prepared by reacting a neutral barium sulphonate of the formula (RSO3)2Ba or [(R)a ASO3]2Ba, wherein R is a cyclic or straight or branched chain, saturated or unsaturated hydrocarbon radical having a molecular weight from 150 to 800, A is an aromatic radical and a  is an integer from 1 to 4, with 1 to 1.5 mols. of barium hydroxide per mol. of neutral sulphonate, reacting the resulting basic sulphonate with 0.5 to 1.0 mol. of CO2 per mol. of excess barium contained in the basic sulphonate, then reacting the product with 1 to 1.5 mols. of barium hydroxide per mol. of original neutral sulphonate and finally reacting with 0.5 to 1 mol. of CO2 per mol. of additional barium incorporated in the basic sulphonate (see Division C2). Specified sulphonates are those derived from white oil alkylated benzene sulphonic acid, dipolypropylene alkylated benzene sulphonic acid, mahogany sulphonic acid and triacontyl sulphonic acid, but additional examples for R and A are given. The base lubricating oils may be mineral or synthetic, for example olefine polymers, alkylene oxide polymers whose terminal groups may be modified by etherification or esterification, dicarboxylic acid esters, liquid esters of phosphorus acids, aryl base-type synthetic oils, e.g. alkyl benzenes, polyphenyls, polyphenyl ethers and indane derivatives, organic silicates and polysiloxanes, many examples being given.  The sulphonates, which may first be prepared as mineral oil concentrates, have oil-thickening properties and may be used with other additives, e.g. detergents and oxidation inhibitors. Specifications 743,842, 744,405 and 790,471 are referred to.