Patent GB-894650-A (GB)
Title: Metal salts of phenols and low molecular weight acids
IPC: C07C51/41
Filed: 1960-03-08
Abstract: Compositions which are suitable for use in the formulation of lubricating oils and greases are prepared by heating a mixture of a phenol and acetic acid (or a hydroxy-, mercapto-, or halosubstituted acetic acid) with an oxide, hydroxide or carbonate of barium, calcium, zinc, magnesium, cadmium, iron, nickel, chromium or cobalt, or by first reacting the metal base with the acetic acid and then heating the acetate with the phenol. The term "phenol" includes alkylphenols, alkylaminophenols, and "bridged phenols" having the structure <FORM:0894650/III/1> wherein R is a C1 to C30 alkyl radical or a halogen atom, a is 0, 1 or 2, b is an integer from 0 to 10, and X is a bridging group comprising carbon or sulphur atoms.  The term "phenol" also includes hydrogenated bridged phenols of the above structure.  In Example 2, a lubricating oil is produced by heating a mixture of dodecylphenol, acetic acid, hydrated lime and a naphthenic type mineral oil to 300 DEG  F. until evolution of water-vapour ceased.  Example 3 gives details of the production of a grease by heating a mixture of p-cresol, acetic acid, hydrated lime and mineral oil.  After the mixture has been cooled, phenyl alpha naphthylamine is added as an oxidation inhibitor.  A synthetic ester oil may be used in place of the mineral oil.  In Example 4, a hightemperature grease is produced by heating a mixture of 2, 6-di-tertiary butyl-4 (N, N-dimethylaminomethyl) phenol, acetic acid, lime, stearic-type fatty acids and mineral oil.  Other alkylated aminophenols which may be used are 2-methyl-4-(di- N, N-butyl-aminomethyl) phenol and m-dimethylamino-phenol.  Examples 5 and 6 relate to the production of greases using, as phenol component of the composition, a carbon-bridged and sulphur-bridged phenol, respectively.  In Example 7, greases are made by heating mixture of a carbon-bridged alkylated phenol, acetic acid, hydroxy-stearic acid, lime and mineral oil.  In Examples 8 and 9, a sulphur-bridged alkylated phenol and a halogenated carbon-bridged phenol, respectively, are employed to make lubricating compositions.  Chromium and barium are employed as the metallic components of the compositions described in Examples 10 and 12, respectively.ALSO:Salts suitable for use in the formulation of lubricants (Group III) are prepared by heating, at 180 DEG C. to 600 DEG C., a mixture of a phenol and acetic acid (or a hydroxy-, mercapto- or halo-substituted acetic acid) with an oxide, hydroxide or carbonate of barium, calcium, zinc, cadmium, iron, nickel, magnesium, chromium, or cobalt, or by first reacting the metal base with the acetic acid and then heating the acetate with the phenol. The term "phenol" includes alkylphenols, alkylamino-phenols, and "bridged phenols" having the structure <FORM:0894650/IV (b)/1> wherein R is a C1 to C30 alkyl radical or a halogen atom, a is 0, 1 or 2, b is an integer from 0 to 10, and X is a bridging group comprising carbon or sulphur atoms.  The term "phenol" also includes hydrogenated bridged phenols of the above structure.  In Example 1, three separate solutions, in ethanol, of dodecyl phenol and chromic acetate, the mol ratio of acetate to phenol being 3 : 1, 6 : 1 and 12 : 1, respectively, are heated between 180 DEG F. and 300 DEG F. until all the ethanol is removed.  The products range from viscous liquids to rubbery-like solids.  In Example 4, a mixture of 2,6-di-tertiarybutyl-4-(N,N-dimethyl-aminomethyl)phenol and acetic acid is added to a mixture of mineral oil, lime and stearic-type fatty acids, and the resulting mixture is heated at 410 DEG F.  The cooled product is a grease.  In Example 7, a mixture of carbon-bridged alkylated phenols is prepared by condensing a C7 aldehyde with a mixture of cresols and xylenols, the condensation being carried out in the presence of an ion-exchange resin at a temperature of 190 DEG C.-230 DEG C. and a pressure of 0.3 mm.Hg. The product is mixed with acetic acid, and then added to a mixture of lime, mineral oil and hydroxy-stearic acid in a steam-heated grease kettle.  The example also refers to the preparation of 1, 1 - bis (4 - hydroxy - 5 - nonylphenyl) iso - octane and 2, 2 - bis (2 - hydroxy - 5 - dodecyl - phenyl)propane.  In Example 8, phenol is alkylated with a trimer of propylene, the resulting nonylphenol is treated with sulphur dichloride to give bis(hydroxy nonylphenyl)sulphide, and this S-bridged phenol is used, together with lime and glacial acetic acid, to prepare a salt.  Example 9 relates to the preparation of a mineral oil solution of a calcium salt of 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane.  Example 10 relates to the preparation of salts obtained by heating bis(hydroxy-dodecylphenyl)sulphide with various proportions of chromic acetate.  Example 11 describes the hydrogenation of 1,1-bis(4-hydroxyphenyl)iso-octane, at 225 DEG C. under a pressure of 550 p.s.i. in the presence of Raney nickel, to give 1,1-bis(4-hydroxycyclohexyl)iso-octane.  This hydrogenated bisphenol is then dissolved in acetic acid, added to a mixture of mineral oil 320 DEG F.  This example also refers to the preparation and hydrated lime; and the mixture is heated at of salts from bis(4-hydroxycyclohexyl)methane.  Example 12 relates to the preparation of a grease composition by mixing acetic acid with bis(4-hydroxycyclohexyl)sulphide, followed by neutralization of the mixture with barium hydroxide in a mineral oil menstruum, and heating to dehydrating temperatures in the range of 300 DEG  to 450 DEG F.