Patent GB-942067-A (GB)
Title: Calcium alkoxide-carbonate complexes, their preparation and use
IPC: F02B3/06
Filed: 1960-04-27
Abstract: Stable dispersions of a basic calcium-containing, inorganic compound in a non-volatile carrier, said inorganic compound being present in the form of particles having a diameter not exceeding about 0.25 micron are prepared by mixing an alcoholic solution of an oil-soluble calcium alkoxide-carbonate complex, as defined below, an oil-soluble dispersing agent, a nonvolatile carrier and an amount of water in excess of that required to hydrolyse the calcium alkoxide-carbonate complex, and then removing the volatile materials (alcohol, solvent and unreacted water).  The calcium alkoxide-carbonate complex is one of formula <FORM:0942067/C1/1> in which x varies from 0.5 to 1.5 and R is a hydrocarbon group which may be substituted by halogen atoms and/or ether groups. Suitable non-volatile solvents include mineral lubricating oils, vegetable oils, animal oils, synthetic oils, dicarboxylic acid esters and esters of phosphorus acids. Suitable dispersing agents are oil-soluble sulphonic acids, carboxylic acids, phosphorus-treated olefines and metal salts thereof.  If desired solvents may be added to reduce the viscosity.  Specifications 789,820, 836,856 and 843,318 are referred to.ALSO:The invention comprises calcium alkoxidecarbonate complexes having the formula. <FORM:0942067/C2/1> in which R is an alkyl group containing 1-6 carbon atoms or a group -CH2CH2OR1, in which R1 is an alkyl group containing 1-4 carbon atoms, and x varies from 0.5 to 1.5, preferably from 0.85 to 1.15.  These complexes and other similar ones may be prepared by reacting calcium, calcium hydride or calcium carbide with an alcohol of formula ROH with the evolution of hydrogen or acetylene, and reacting the resulting calcium alkoxide with carbon dioxide, R being a hydrocarbon radical which may be substituted by halogen atoms and/or ether groups.  Suitable alcohols are those having 3-8 carbon atoms, e.g. isobutanol; isopentanol; 2-ethyl butanol; 2-ethyl hexanol; ethylene glycol monomethyl, monoethyl, monobutyl and monophenyl ethers; diethylene glycol monomethyl and monoethyl ethers; 2-chloroethanol; 2-chlorobutanol; 2-bromopentanol; 2,2,3,3-tetrafluoropropanol; furfuryl alcohol; and tetrahydrofurfuryl alcohol.  As a modification of the above process methyl alcohol may be reacted with calcium, calcium hydrides or calcium acetylide to give calcium methoxide which is transalcoholised to calcium isobutoxide which is then reacted with carbon dioxide.  Excess alcohol present acts as a solvent for the complex.  In some cases an acidic catalyst is necessary for the reaction with carbon dioxide. Specifications 789,820, 836,856 and 843,318 are referred to.ALSO:Stable dispersions of a basic calcium-containing, inorganic compound in a nonvolatile carrier, said inorganic compound being present in the form of particles having a diameter not exceeding about 0.25 micron are prepared by mixing an alcoholic solution of an oil-soluble calcium alkoxide-carbonate complex, as defined below, an oil-soluble dispersing agent, a non-volatile carrier and an amount of water in excess of that required to hydrolyse the calcium alkoxide-carbonate complex and then removing the volatile materials (alcohol, solvent and unreacted water).  The calcium alkoxide-carbonate complex is one of formula <FORM:0942067/C3/1> in which x varies from 0.5 to 1.5 and R is a hydrocarbon group which may be substituted by halogen atoms and/or ether groups. Suitable non-volatile carriers include mineral lubricating oils; vegetable oils; animal oils; synthetic oils, e.g. polymers of propylene, polyoxyalkylenes, polyoxypropylene, dicarboxylic acid esters, e.g. adipic and azelaic esters of butyl, 2-ethyl hexyl and dodecyl alcohols, and esters of phosphorus acids such as decane phosphoric acid and tricresyl phosphate.  If desired, solvents, e.g. petroleum naphtha, hexane, heptane, octane, benzene, toluene or xylene, may be added to reduce the viscosity.  Suitable oil-soluble dispersing agents are the oil-soluble sulphonic acids, carboxylic acids, phosphorus sulphide-treated olefines, and metal salts thereof. Suitable sulphonates include alkyl sulphonates, alkaryl sulphonates and mahogany or natural soaps.  The dispersions may be used in the range of 1-20% by weight in motor lubricating oils, and 5-25% in marine diesel oils. Specifications 789,820, 836,856 and 843,318 are referred to.