Patent GB-1038263-A (GB)
Title: An oil-soluble composition comprising a carbonated metal salt of a sulphonic acid
IPC: C10M159/24
Filed: 1964-02-05
Abstract: A lubricating composition comprises a major proportion of a lubricating oil and a minor proportion of an oil-soluble composition which comprises a carbonated, basic alkaline earth metal salt of a bright stock sulphonic acid (see Division C2), the metal salt having a metal ratio of at least about 3.  The concentration of the carbonated, basic metal salts in the lubricating compositions may range from about 0.1% to about 30% by weight.  The mineral oils useful as the lubricating oil base are preferably refined oils having viscosity values ranging from about 50 S.U.S. at 100 DEG  F. to about 500 S.U.S. at 210 DEG  F.  If the carbonated, basic metal salt is prepared in a limited amount of mineral oil, the concentrate obtained may be diluted with additional amounts of mineral oil to give the required lubricating composition.  The concentrate may also contain other additives. Other additives which may be present are supplementary detergent additives, rust-inhibiting agents, corrosion-inhibiting agents, extreme pressure agents, anti-foam agents, pour-point depressing agents, viscosity index improving agents, metal-deactivating agents, and oxidation-inhibiting agents. Group II metal phosphorodithioates are desirable for use in the lubricating compositions, the dialkylphosphorodithioates of zinc, calcium and barium being preferred.  The alkyl radicals usually contain an average of at least 7.6 aliphatic carbon atoms per phosphorus atom.  Other inhibiting agents include the oil-soluble alkaline earth metal salts of alkylated phenolic compounds such as alkyl-phenols, alkylnaphthols, sulphurized alkyl-phenols and naphthols, and condensation products of the alkylated phenolic compounds with aldehydes or ketones.  The alkyl radical in the phenolic compounds should contain at least 7 carbon atoms.  Also the basic metal salts of the above alkylated phenolic compounds, prepared by heating a mixture of an alkylated phenolic compound with an excess of an alkaline earth metal base or by carbonating at a temperature of about 100-250 DEG  C. may be used.  Other inhibiting agents useful are sulphurized or phosphosulphurized hydrocarbons or fatty materials such as dibutyl tetrasulphide, dipentyl disulphide, the reaction products of alphapinene with sulphur or P2S5, of terpentine with S or P2S5, of methyl oleate with P4S6 and of sperm oil with S.  Organic phosphites such as dialkyl (including cycloalkyl) phosphites and diaryl phosphites are also useful. Further detergent additives may be acylated alkylene amines.  A preferred class of acylated amines are the reaction products of an ethylene amine such as ethylene diamine, diethylene triamine, tetraethylene pentamine, hexamethylene heptamine, or triethylene tetramine with a hydrocarbon substituted succinic acid or anhydride in which the hydrocarbon substituent contains at least 50 aliphatic carbon atoms.  In the examples, the concentrate of the carbonated, basic calcium bright stock sulphonate is blended with (1) SAE20 mineral oil, (2) SAE30 mineral oil and zinc di-octylphosphorodithioate, (3) SAE90 mineral oil, zinc dicyclohexylphosphorodithioate and an acylated amine obtained by heating 1 mole of a polyisobutene (M.W. of 1000)-substituted succinic anhydride with 0.4 mole of tetraethylene pentamine at 150-220 DEG  C. and removing the water formed thereby; (4) SAE30 mineral oil, calcium salt of 2,21-methylene - bis - (4 - heptylphenol), and polyisobutene (M.W. of 750)-substituted succinimide of N-aminoethyl piperazine; (5) SAE10 mineral oil and di-benzyl disulphide; (6) SAE30 mineral oil; and (7) SAE40 mineral oil, dibutyl tetrasulphide, an ashless detergent obtained by heating equi-molar amounts of polyisoprene (M.W. of 1500)-substituted succinic acid and ethylene diamine at 150-250 DEG  C. and removing the water formed thereby.ALSO:The invention comprises an oil-soluble composition suitable for use as a detergent in lubricating oils comprising a carbonated, basic alkaline earth metal salt of a bright stock sulphonic acid, or of a mixture of at least 50% by weight of a bright stock sulphonic acid and not more than 50% of a carboxylic acid having at least 12 aliphatic carbon atoms, the metal salt having a metal ratio of at least 3.  The term " metal ratio " is used to designate the ratio of the total equivalents of the metal in the metal salt to the equivalents of metal in the form of a normal salt.  It may be obtained by carbonating a substantially anhydrous mixture of the acid reactant with at least about three equivalents of an alkaline earth metal base per equivalent of acid in the presence of a promoting agent.  The metal base may be an alkaline earth metal oxide, hydroxide, bicarbonate, sulphide, mercaptide, hydride, alcoholate or phenate.  The alkaline earth metal may be Mg, Ca, Sr, or Ba, but is preferably calcium. The carboxylic acids which may be used together with the bright stock sulphonic acids may be substituted, unsubstituted aliphatic, or aliphatically substituted aromatic acids having at least 12 aliphatic carbon atoms, such as palmitic acid, stearic acid, myristic acid, oleic acid, linoleic acid, behenic acid, hexatria-contanoic acid, stearyl benzoic acid, wax (eicosane) substituted naphthoic acid, dilauryl decahydronaphthalene carboxylic acid, dido-decyltetralin carboxylic acid, dioctyl-cyclohexane carboxylic acid, the acids obtained by hydrolysis of sperm oil, tall oil or other fatty esters, alkenyl succinic acids or anhydrides in which the alkenyl group contains at least 12 carbon atoms such as the product of the reaction of maleic acid or anhydride with a polyisobutene having a M.W. of about 700-1000. The promoting agent may be an alcohol including polyhydric alcohols and heterocyclic alcohols or a phenol. Alcohols having up to 12 carbon atoms, phenols and alkylated phenols having one to three alkyl substituents each of which has up to 50 carbon atoms and mixtures thereof are preferred.  The amount of promoting agent to be used may be from 0.1 to 10 equivalents or more per equivalent of the acid reactant, preferably from about 0.25 to 5 equivalents.  It is desirable to use the above hydroxy compounds in combination with from about 0.1% to 5% based on the weight of the carbonation mixture of an inorganic halide such as ammonium chloride or bromide, or an alkali metal or alkaline earth metal halide.  The carbonation temperature depends on the promoting agent, when a phenol is used the temperature may be from 80 DEG  to 300 DEG  C. preferably from 100 DEG  to 200 DEG  C., and when an alcohol is used a temperature from 20 DEG  to 100 DEG  C. is generally suitable. The promoting agent may be removed by distillation, after carbonation, if it is a volatile substance otherwise it is allowed to remain in the product.  Generally, it is convenient to prepare the carbonated, basic metal salt in a mineral oil so that the product is a fluid oil solution or concentrate which readily mixes with additional quantities of mineral oil to give the required lubricating composition.  The carbonation may be carried out in a solvent such as mineral oil, hexane, naphtha, dodecane, benzene, toluene, xylene.  It may also be a polar substituted hydrocarbon such as chlorobenzene, diphenyl oxide or nitrobenzene. Examples are given for the carbonation of calcium bright stock sulphonate (1) in toluene as solvent in the presence of methanol, isooctanol and ammonium chloride as promoter (2) as in (1) except that ammonium chloride is replaced by calcium chloride (3) as in (2) except that the calcium hydroxide is added in stages to the bright stock sulphonic acid, (4) as in (3) except that lime is added in 4 portions followed by carbonation (5) in admixture with distilled tall oil acid, in mineral oil as solvent, in the presence of methanol, octanol and calcium chloride as promoter, the alkaline earth metal base being calcium hydroxide (6) as in (5) except that toluene is present in addition as solvent (7) as in (6) except that naphthenic acid is used in place of distilled tall oil acid and (8) as in (1) except that ammonium chloride is absent.  The products may be used as additives for lubricating oils (see Division C5).