Patent GB-844335-A (GB)
Title: High barium content complex salts of sulphonic acids
IPC: C10L1/24
Filed: 1958-04-01
Abstract: Complex carbonated barium sulphonates, which contain a high percentage of barium, are obtained by reacting a solution, in hydrocarbon oil, of a basic barium sulphonate of the general formula: <FORM:0844335/IV(b)/1> with carbon dioxide followed by basic barium methylate.  In the above formula, A is a benzene or naphthalene nucleus, R is an alkyl radical containing 8 to 24 carbon atoms, and n is 1 to 5.  The oil solution is maintained at a temperature of from about 150 DEG C. to about 250 DEG C. while the carbon dioxide is passed into it, and the treatment is continued until at least 1 mol of CO2 has reacted with each mol of basic barium sulphonate.  The reaction-mixture is then cooled to about 25 DEG -60 DEG C., and barium methylate BaOH(OCH3) is added in an amount sufficient to provide at least 1 equivalent of barium per mol of basic barium sulphonate.  The product contains 3 equivalents of barium, and may be subjected to further carbonation and barium methylate treatments to obtain salts of higher barium content.  Salts having 14 equivalents of barium per equivalent of sulphonic acid have been prepared, the ratio of combined CO2 to Ba in the salt being approximately 1:1.  The products are useful as addition agents for lubricating and fuel oils (see Group III).  Suitable starting materials are produced by the action of barium hydroxide on acids obtained by sulphonation of petroleum or synthetic alkyl-substituted benzenes and naphthalenes wherein the alkyl groups contain 8 to 24 carbon atoms.  In an example, paraffin wax having an average of 24 carbon atoms per molecule is chlorinated at about 100 DEG C. until its weight has increased by about 12 DEG .  The chlorowax is reacted, at 60 DEG -100 DEG C., with benzene in such proportions that there is 1 mol of benzene per 2 atomic proportions of chlorine in the chlorowax, the reaction being catalysed by aluminium chloride.  The waxbenzene is reacted with oleum, and the product is poured into water.  The mixture is stirred with a solvent refined Mid-Continent oil, and allowed to stand; the water is then drained-off.  Barium hydroxide octahydrate is added to the solution of the wax-benzene sulphonic acid, and the temperature of the mixture is slowly raised to 150 DEG C. and held there for 1 hour.  The solution of the basic barium salt is filtered through diatomaceous clay, and diluted with mineral oil to provide a solution (Product A) containing 7,5% by weight of barium.  This solution is blown with CO2 for 3 hours at 200 DEG C. The mixture is cooled to 60 DEG C., and a solution of barium methylate is methanol is added.  The mixture is then heated to 175 DEG C. to eliminate uncombined methanol, and filtered.  The product is an oil blend containing 10% of barium. In Example 2, Product A is subjected to a two-stage process, of carbonation and barium methylate addition, to yield an oil blend p  containing 13% of barium.  In Example 4, the oil blend containing 10% of barium obtained in the first example is subjected to a three-stage process, of carbonation and barium addition, to yield an oil blend containing 18% of barium. Example 6 describes the preparation, from Product A, of an oil blend containing 31,5% of barium by a twelve-stage process of carbonation and barium-addition.ALSO:Hydrocarbon oils (e.g. mineral lubricating oils or fuel oils) contain dissolved therein complex carbonated barium sulphonates containing a high percentage (viz. 10 to 30%) of barium.  The additives are prepared by reacting a hydrocarbon oil solution of a basic barium salt of an alkylated aromatic sulphonic acid first with carbon dioxide and then with basic barium methylate (see Group IV(b)).  In examples, the starting material is a mineral oil solution of the basic barium salt of a C24-alkyl benzene sulphonic acid, from which oil blends containing 10, 13, 16, 18, 21 and 31.5% barium are obtained, although basic barium salts of petroleum sulphonic acids are also mentioned.  The Specification gives the results of comparative tests (showing the sludge-inhibiting and wear-inhibiting properties of the additives) carried out on gasoline- and diesel-engines using mineral lubricating oils with and without minor proportions (3 to 6%) of one or other of the high-barium oil blends referred to above.  The Specification also includes the results of tests which evaluate the ability of the complex barium salts to prevent the deterioration of fuel oil on storage, and as anti-screen clogging agents in contaminated fuel oil. The fuel oil employed comprised a blend of 60% catalytically cracked component and 40% straight-run component and had a boiling-range of approximately 320 DEG  to 640 DEG F.