Patent GB-684155-A (GB)
Title: Manufacture of metal salts of organic acids
IPC: C07C37/66
Filed: 1949-06-20
Abstract: Polyvalent metal salts of phenols, carboxylic acids and organo-substituted acids of phosphorus are obtained by reacting the phenol or acid with a polyvalent metal basic compound in the presence of a polyhydric alcohol.  The latter is used in sufficient amount to cause substantial contact between the reactants, e.g. from 0.2 to 10.0 (preferably 0.75 to 2.0) times the weight of phenol or acid.  In the preferred method the basic compound is dispersed in the polyhydric alcohol and then contacted with the phenol or acid; the water of reaction is then removed with or without some polyhydric alcohol.  A higher-boiling liquid such as a mineral oil is then added and the remainder of the alcohol removed and, if desired, recycled. Suitable alcohols are ethylene glycol, propylene glycol, butanediol-2 : 3, pentanediols-2 : 3 and 2 : 4, 2-methylbutanediols-1 : 3, 2 : 4 and 3 : 4, and glycerol.  Suitable basic compounds are the oxides and hydroxides of magnesium, calcium, barium, strontium, lead and thallium.  Examples show the production of calcium "alkyl"-phenate, barium "alkyl"-phenate, calcium p-tert-amyl-phenate, lead "lkyl"-phenate and magnesium "lkyl"-phenate, the products being obtained as solutions in mineral oils and in some cases are further reacted with sulphur to produce lubricating oil additives.  The "alkyl"-phenol used was a mixture where the side-chains contained 14-16 carbon atoms. Samples have been furnished under Sect. 2 (5) of (1) calcium stearate, (2) a mixture of calcium mono- and di-cetyl phosphates, (3) calcium O : O-dibutyldithiophosphate, and (4) calcium "white oil" phosphonate, prepared by the method of the invention. The acidic starting materials are of the formula RX, where R is an organic radical and may be aliphatic, alicyclic, aromatic or aralkyl, and X is a phenolic hydroxyl group, a carboxylic acid group or the residue of a phosphorus-containing acid.  Thus RX may be ethylphenol, tert-amylphenol, octylphenol, dodecylphenol, cetylphenol, caproic acid, stearic acid, palmitic acid, naphthenic acid, mono- and di-cetylphosphoric acids, cetane phosphonic acid and its monoethyl ester, dicetylphosphinic acid, dicetyl phosphite, dicetylphosphinous acid, cetane phosphonous acid and its monobutyl ester and sulphur and selenium derivatives of these.  According to the Specification as open to inspection under Sect. 91, X in the above formula may be any group containing an acidic hydrogen atom.  In addition to the above there are specified mercaptans, hydroselenides, sulphuric acid monoesters, sulphonic acids (e.g. dodecane sulphonic acid), sulphinic acids (e.g. dicetylsulphinic acid-sic-), arsonic acids (dodecane arsonic acid), arsinic acids (dilaurylarsinic acid), arsenic acid esters (mono- and di-cetyl), arsonous acids (octane arsonous acid) and their monoesters, arsenous acid esters, boric acid esters, boronic acids (cetane boronic acid), borinic acids (dicetylborinic acid) and esters and sulphur and selenium derivatives of these.  A further example is given of the preparation of calcium "alkyl"-benzene sulphonate, the side-chain having 14-16 carbon atoms (mixture).  This subject-matter does not appear in the Specification as accepted.ALSO:Lubricating oil additives are made by reacting a polyvalent metal basic compound with a phenol, carboxylic acid or organo-substituted phosphorus acid in the presence of a polyhydric alcohol, adding a mineral oil and removing the polyhydric alcohol and water of reaction.  The product may be sulphurized if desired. Examples show the production of mineral oil solutions of calcium "alkyl"-phenate, barium "alkyl"-phenate, calcium p-tert-amylphenate, lead "alkyl"-phenate and magnesium "alkyl"-phenate, with or without sulphurization.  The "alkyl"-phenol used was a mixture where the side-chains contained 14-16 carbon atoms.  Other specified metals are strontium and thallium.  Samples have been furnished under Sect. 2 (5) of calcium stearate, a mixture of calcium mono- and di-cetyl phosphates, calcium O:: O-dibutyldithiophosphate and calcium "white oil" phosphonate.  The process is stated to be applicable also to phosphinic acids, phosphite partial esters, phosphinous acids, phosphorous acids and partial esters and p  sulphur and selenium derivatives of phosphorus acids.  According to the Specification as open to inspection under Sect. 91, the process may be applied to mercaptans, hydroselenides, sulphuric acid monoesters, sulphonic acids, sulphinic acids and organic derivatives of arsenic and boron acids, a list of such being given.  A further example is given of the production of a mineral oil solution of calcium "alkyl"-benzene sulphonate, the alkyl group having 14-16 carbon atoms.  This subject-matter does not appear in the Specification as accepted.