Patent GB-778651-A (GB)
Title: Metal salts of carboxylic acids and compositions containing them
IPC: C10M117/02
Filed: 1956-03-16
Abstract: Silicone oils are thickened to greases with an additive comprising at least one metal salt of a C1-C3 carboxylic acid and at least one metal salt of a C7-C10 carboxylic acid, the molar ratio of the first acid to the second being from 2:1 to 40:1, and no aluminium salt or soap being present.  The salts may be present as a mixture of a complex depending upon the temperature used in their preparation. At 150-200 DEG  F., a mixture of hydrous salts having 0.5-15 per cent water is formed; at 250-350 DEG  F., an anhydrous mixture is obtained; and above 400 DEG  F. mixed salt complexes are formed.  The C1-C3 acids include formic, acetic propionic, lactic, acrylic or mixtures and, may have a saponification number above 540.  The C7-C10 acids may be saturated or unsaturated, straight or branched chain or mixtures and may have a saponification number of 310-440.  Examples are caprylic, heptanoic, 2-ethyl hexanoic, 5-methyl-2-hexanoic, pelargonic, capric, and C8 and C10 oxo acids.  The metals include Ca, Sr, Mg, Ba, especially for grease thickeners, heavy metals of Groups 1, 2 and 4, especially Cu, Zn and Pb, alone or with alkaline earths, Co, Ni, Cr and Mn.  The salts may be prepared by co-neutralization of the acids with the metal hydroxides or carbonates, especially in the oil or liquid in which the salt or complex is to be used.  Part of the salt may, however, be preformed.  The salts may be incorporated in amounts of 5-49 per cent.  In an example, methyl phenyl polysiloxanes or methyl silicone are thickened with calcium acetate-caprylate.ALSO:An oil additive comprises at least one metal salt of a C1-C3 carboxylic acid and at least one metal salt of a C7-C10 carboxylic acid, the molarratio of the first acid to the second being from 2 : 1 to 40 : 1, and no aluminium salt or soap being present.  The salts may be present as a mixture or a complex depending upon the temperature used in their preparation.  At 150-200 DEG  F. a mixture of hydrous salts having 0.5-15 per cent water is formed; at 250-350 DEG  F. an anhydrous mixture is obtained; and above 400 DEG  F. mixed salt complexes are formed.  The C1-C3 acids include formic, acetic, propionic, lactic, acrylic or mixtures and may have a saponification number above 540.  The C7-C10 acids may be saturated or unsaturated, straight or branched chain or mixtures and may have a saponification number of 310-440. Examples are caprylic, heptanoic, 2-ethyl hexanoic, 5 - methyl - 2 - hexanoic, pelargonic, capric, and C8 and C10 oxo acids.  The metals include Ca, Sr, Mg, Ba, especially for grease thickeners, heavy metals of Groups 1, 2 and 4, especially Cu, Zn and Pb, alone or with alkaline earths, Co, Ni, Cr and Mn.  The salts may be prepared by co-neutralization of the acids with the metal hydroxides or carbonates, especially in the oil or liquid in which the salt or complex is to be used.  Part of the salt may, however, be preformed.  The product may be isolated from the medium by solvent extraction of the latter.  For example, heptane is used to dissolve mineral oil.  The salts may be incorporated in mineral or synthetic oils (see Group III).  In examples: (1) mineral oil base greases are prepared by heating the oil and hydrated lime with acetic and caprylic acids in various ratios at up to 480 DEG  F. followed by cooling, adding phenyl a -naphthylamine, and homogenizing; (2) capric or caprylic and acetic acids are used in preparing similar greases; (3) C8 or C10 oxo acids, and 2-ethyl hexanoic acids are used with acetic, the oxo acids yielding soft greases which may be used as extreme pressure additives for simple soap thickened greases or blended with complex soda soap grease (prepared from rapeseed oil and mineral oil); (4) commercial caprylic which contains capric and caproic acids is used; (5) di-iso-octyl azelate is used as the medium thickened to a grease by calcium acetate-caprylate; (6) methyl phenyl polysiloxanes or methyl silicone are similarly thickened; (7) barium or mixed barium, calcium salts are used which may be prepared in situ in the mineral oil or in part preformed; (12) a blended grease is prepared from 75 per cent calcium soap-calcium acetate thickened mineral oil and 25 per cent calcium acetate-caprylate thickened oil.  Other examples of similar preparations of greases and blends with mineral oils are given and their properties described.ALSO:An oil additive comprises at least one metal salt of a C1-C3 carboxylic acid and at least one metal salt of a C7-C10 carboxylic acid, the molar ratio of the first acid to the second being from 2 : 1 to 40 : 1, and no aluminium salt or soap being present.  The salts may be present as a mixture or a complex depending upon the temperature used in their preparation.  At 150-200 DEG F., a mixture of hydrous salts having 0.5-15 per cent water is formed; at 250-350 DEG F., an anhydrous mixture is obtained; and above 400 DEG F. mixed salt complexes are formed.  The C1-C3 acids include formic, acetic, propionic, lactic, acrylic or mixtures and may have a saponification number above 540.  The C7-C10 acids may be saturated or unsaturated, straight or branched chain or mixtures and may have a saponification number of 310-440. Examples are caprylic, heptanoic, 2-ethyl hexanoic, 5-methyl-2-hexanoic, pelargonic, capric, and C8 and C10 oxo acids.  The metals include Ca, Sr, Mg, Ba, especially for grease thickeners, heavy metals of Groups 1, 2, and 4, especially Cu, Zn, and Pb, alone or with alkaline earths, Co, Ni, Cr, and Mn.  The salts may be prepared by co-neutralization of the acids with the metal hydroxides or carbonates, especially in the oil or liquid in which the salt or complex is to be used. Part of the salt may, however, be preformed.  The salts may be incorporated in mineral or synthetic oils in amounts of 5-49 per cent to give greases or in amounts of 0.02-4 per cent, for example, as anti-corrosives especially for residual fuel oils of high ash or vanadium content. Synthetic oils include hydrocarbon, ester, formal, mercaptal, polyalkyleneoxide or silicone types. Lubricating, metal cutting or drawing and like oils are referred to.  Additives such as inhibitors, deactivators, extreme pressure agents, dyes and deodorants may also be incorporated.  In examples: (1) mineral oil base greases are prepared by heating the oil and hydrated lime with acetic and caprylic acid in various ratios at up to 480 DEG F. followed by cooling, adding phenyl  -naphthylamine, and homogenizing; (2) capric or caprylic and acetic acids are used in preparing similar greases; (3) C8 or C10 oxo acids and 2-ethyl hexanoic acids are used with acetic, the oxo acids yielding soft greases which may be used as extreme pressure additives for simple soap thickened greases or blended with complex soda soap grease (prepared from rapeseed oil and mineral oil); (4) commercial caprylic which contains capric and caproic acids is used; (5) di-isooctyl azelate is used as the medium thickened to a grease by calcium acetate-caprylate; (6) methyl phenyl polysiloxanes or methyl silicone are similarly thickened; (7) barium or mixed barium, calcium salts are used which may be prepared in situ in the mineral oil or in part preformed: (12) a blended grease is prepared from 75 per cent calcium soapcalcium acetate thickened mineral oil and 25 per cent calcium acetate-caprylate thickened oil. Other examples of similar preparations of greases and blends with mineral oils are given and the properties described.