Patent GB-599729-A (GB)
Title: An improved manufacture of the metal derivatives of alkyl phenols and their sulfide, selenide and telluride derivatives
IPC: C07C323/20
Filed: 1944-10-25
Abstract: Metal salts of alkyl phenols or alkyl phenol sulphides, selenides or tellurides, intended as lubricating oil additives, are rendered less sensitive to water by blowing a solution thereof in an inert non-aqueous solvent, especially a mineral lubricating oil, with a weakly acid gas, e.g., carbon dioxide or hydrogen sulphide, in the presence of or after pretreatment of the salt with water or steam. The amount of acid gas is advantageously less than 25 (preferably less than 5) per cent. and that of water or steam less than 20 (preferably less than 5) per cent by weight of the amount of salt present, and the treatment may be carried out at 20-200 DEG C. (preferably at 75-150 DEG C.) for 1-10 (preferably 2-6) hours, and is preferably followed by filtration, for which a filter aid such as an inert diatomaceous earth or an active clay may be used.  The process is applicable to monovalent or preferably polyvalent metal (e.g., sodium, potassium, lithium, aluminium, cobalt, chromium, magnesium, manganese, nickel, lead, tin, zinc, copper, iron, cadmium, calcium and especially barium) derivatives of compounds of the types HOC6H4R, HOC6H3RR1, HOC6H2RR1R11, HO-(R)C6H3 - O - C6H3(R)-OH, HO-(R)C6H3-O-CH2C6H4OH, HO-(R)C6H3CH2-O-C6H3(R1)-OH, HOC10H6R and HOC10H5RR1, and especially of the types HO-(R)C6H3-S-C6H3(R)-OH, HO-(R)C6H3-S2-C6H3(R)-OH, HO-(R)C6H3-S-C4H9, HO-(R)C6H3-S-CH2C6H5, HO-(R)C6H3CH2-S-CH2C6H3(R)-OH, HO-(R)C6H3-S-CH2C6H3(R)-OH, HO-(R)C6H3-S-CnHmOH, HO-(R)C6H3-S-C6H3(R)-CnHmOH, HO-(OR)C6H3-S-C6H3(OR)-OH, HO - (OR)C6H3-S-C6H2(R1) (OR) - OH, (HO)2(R)C6H2 - S - C6H2(R)(OH)2, HO-(R)-C6H2-S-C6H2(R)-OH, HO-(R)C6H3-S-C6H3(R)-OR, HO-(R)C6H3-S-C6H4R, HO-(R)C6H3-S-C6H3R1R11 and HO - R(COR)C6H2 - S - C6H2(R)(COR)-OH (wherein R, R1 and R11 represent alkyl groups, preferably containing at least 4 (e.g. 8-24) carbon atoms), and more specifically to compounds of the formulae <FORM:0599729/III/1> <FORM:0599729/III/2> <FORM:0599729/III/3> <FORM:0599729/III/4> or <FORM:0599729/III/5> (e.g. the barium salts of p-tert.-octylphenol, octadecyl phenol, 2:4-di-tert. amylphenol, tert.-octylphenol sulphide, 2:4-di-tert.-amylphenol sulphide or tert.-amylphenol disulphides), also calcium and aluminium p-tert.-amylphenol sulphide, tin salts of wax alkylated salicylic acid sulphide, magnesium p-tert.-octylphenyl sulphide and barium salts of C16-C20 branched chain alkyl phenol sulphides prepared from phenols alkylated with refinery butene polymers.  Tables show the effect of variations in the amount of water or steam and carbon dioxide and of temperature and time of treatment on products obtained by treatment of a solution of p-tert.-octylphenol sulphide in lubricating oil with various quantities of barium hydroxide.ALSO:Metal salts of alkyl phenols or alkyl phenol sulphides, selenides or tellurides, intended as lubricating oil additives, are rendered less sensitive to water by blowing a solution thereof in an inert non-aqueous solvent (e.g. a mineral lubricating oil) with a weakly acid gas (e.g. carbon dioxide or hydrogen sulphide), in the presence of or after pretreatment of the salt with water or steam.  The amount of acid gas is advantageously less than 25 (preferably less than 5) per cent and that of water or steam less than 20 (preferably less than 5) per cent by weight of the amount of salt present, and the treatment may be carried out at 20-200 DEG  C. (preferably at 75-150 DEG  C.) for 1-10 (preferably 2-6) hours, and is preferably followed by filtration, for which a filter aid such as an inert diatomaceous earth or an active clay may be used. The process is applicable to monovalent or preferably polyvalent metal (e.g. sodium, potassium, lithium, aluminium, cobalt, chromium, magnesium, manganese, nickel, lead, tin, zinc, copper, iron cadmium, calcium and especially barium) derivatives of compounds of the types <FORM:0599729/IV/1> and HOC10H5RR1, and especially of the types <FORM:0599729/IV/2> and <FORM:0599729/IV/3> (wherein R, R1 and R11 represent alkyl groups, preferably containing at least 4, e.g. 8-24, carbon atoms), and more specifically to compounds of the formul <FORM:0599729/IV/4> or Ba(OC6H3Cn H2nn1)2S2 (e.g. the barium salts of p-tert.-octylphenol, octadecylphenol, 2 : 4-di-tert.-amylphenol, tert.-octylphenol sulphide, 2 : 4-di-tert.-amylphenol sulphide or tert.-amylphenol disulphides), also calcium and aluminium p-tert.-amylphenol sulphide, tin salts of wax alkylated salicylic acid sulphide, magnesium p-tert.-octylphenol sulphide, and barium salts of C16-C20 branched chain alkyl phenol sulphides prepared from phenols alkylated with refinery butene polymers. The metal salt is advantageously prepared by treating a solution of the phenolic compound in the insert solvent with an oxide or hydroxide of the metal in an amount not more than 5 per cent in excess of that required for complete neutralization of the phenolic compound, which operation may be carried out, preferably with stirring, at about 20-200 DEG  C., preferably about 90-175 DEG  C., if desired in the presence of additives such as higher aliphatic alcohols (e.g. stearyl alcohol) or aliphatic nitriles used as defoamers, plasticizers, mutual solvents or detergency promoters.  Alternatively the salt may be made by double decomposition from another salt of the phenol (e.g. by treating a sodium salt with barium bromide), in which case the process of the invention may be applied either to the first or the second salt or to both.  Tables show the effect of variations in the amount of water or steam and carbon dioxide and of temperature and time of treatment on products obtained by treatment of a solution of p-tert.-octylphenol sulphide in lubricating oil with various quantities of barium hydroxide.  Alkyl phenol sulphides may be made by the action of a sulphurizing agent, preferably a sulphur halide, e.g. SCl2 or S2Cl2, on alkylated hydroxy aromatic compounds, e.g. on tert.-octylphenol (obtainable by catalytic alkylation of phenol with di-isobutylene) to produce tert.-octylphenol sulphide, or on other alkylphenols, dialkylphenols (e.g. 2 : 4-di-tert.-butylphenol, 2 : 4- or 2 : 6-diamylphenol or di-tert.-octylphenol), or mixtures of phenols, e.g. crude petroleum phenols or crude phenolic materials of coal tar origin such as further alkylated tricresol.