Patent GB-722064-A (GB)
Title: Improvements in or relating to thickened oleaginous compositions
IPC: C10M169/00
Filed: 1952-07-30
Abstract: Anionic surface-active agents comprise alkenyl- or alkyl-substituted aliphatic dicarboxylic acids, prepared by alkylation of such acids as fumaric, succinic, maleic, citraconic, gluconic or adipic acids, or by condensing a polymer of a lower olefin such as ethylene, propylene, butylene, or a higher olefin derived by cracking paraffin wax, with maleic anhydride and hydrolysing the product to the corresponding alkenyl succinic acids.  A cationic surface-active agent may be prepared by condensng epichlorohydrin with ammonia, and converting to a partial amide by reaction with a compound having a hydrophobic anion, e.g. tall oil.  Epichlorohydrin may be replaced by mono-haloepoxyalkanes, mono-halodihydroxyalkanes and dihalohydrins; examples are 2 : 3-epoxy-4-chlorobutane, 1 : 2-dichloro-3-propanol, 1 : 3-dichloro - 2 - propanol, 2 - chloro - 1 : 3 - dipropanol and 1-chloro-2 : 3-dipropanol. Specification 695,309 is referred to.ALSO:A non-aqueous composition comprises a liquid oleaginous material, an inorganic colloidal gelling agent in a proportion which is at least sufficient to thicken the oleaginous material, a minor proportion of a cationic surface-active agent and a minor proportion of a non-metallic anionic surface-active agent.  The oleaginous material may be a mineral lubricating oil; a synthetic hydrocarbon lubricating oil made by the Fischer-Tropsch, Synthol, Synthine, Bergius and Voltolisation Processes; an organic ester lubricating oil, e.g. esters of organic mono- and di-carboxylic acids and inorganic acids such as acids of phosphorus; polymers and copolymers of alkylene glycols; copolymers prepared from epoxides; sulphur-containing polymers; polymers from oxygen - containing heterocyclic compounds; organic silicon containing polymers; and chlorinated diphenyls.  The colloidal gelling agent may be amorphous e.g. silica, alumina, magnesia, lime, copper sulphide, calcium sulphate and manganese phosphate; a crystalline clay, such as the montmorillonites e.g. sodium, potassium, lithium, bentonites, Wyoming bentonite, magnesium bentonite, Hectorate and saponite; Attipulgite, zeolites and Fuller's earth. The clays may be converted to gelling agents by ion-exchange with a cationic surface active agent; such as an onium salt, e.g. an ammonium salt bearing at least one hydrocarbon radical having at least 10 carbon atoms in the molecule, or a salt of an amine, or an analogue or homologue or an amine salt or quaternary ammonium compound.  The clays may also be treated by the adsorption of surface-active agents.  The cationic surface active agents used in the compositions of the invention may be amines or ammonium, phosphonium, arsonium, stibonium, oxonium, sulphonium or selenonium compounds.  Aliphatic amines having 8 to 36 carbon atoms, such as octadecyl, dodecyl and hexadecyl amines, and aliphatic hydroxy amines in which the number of hydroxy and amino groups is at least 3, are preferred.  The partial amides of polyhydroxy alkylene polyamines such as the partial amide of the condensation product of epichlorohydrin and ammonia, may also be used.  Partial amides of polyalkylene polyamides, such as the half amide of oleic acid and ethylenediamine, and heterocyclic amines containing a hydrophobic radical, such as substituted imidazolines, may be used.  Further cationic surface-active agents are triphenyl lauryl phosphonium bromide, didodecyl ethyl sulphonium bromide, decyl triphenyl arsonium chloride, decyl triphenyl stibonium iodide, dodecyl ammonium acetate, dimethyl dicetyl ammonium bromide.  The anionic surface-active agents which may be used in the composition include saturated or unsaturated fatty acids having 8 to 32, preferably 12 to 24, carbon atoms in the molecule, such as oleic, linoleic, linolenic, palmitic, myristic, arachidic and behenic acids.  Hydroxy fatty acids, such as 9-, 10-, 11-, 12-, or 13- hydroxy stearic acid, 10- or 15-hydroxy palmitic acid, 1-hydroxy behenic acid, 10-hydroxy myristic acid, 5:6-dihydroxy stearic acid, and 2:11-dihydroxy palmitic acid; also alkenyl- or alkyl-substituted aliphatic dicarboxylic acids such as fumaric, succinic, maleic, citraconic, gluconic or adipic acids may be used; the alkyl or alkenyl radicals should contain 8 to 25, preferably 12 to 18, carbon atoms.  Further anionic surface-active agents include oleophilic sulphonic acids having molecular weights above 300, preferably between 350 and 600; and alicyclic non-aromatic dicarboxylic acids such as those prepared by dimerization of unsaturated fatty acids and analogues thereof.  Another suitable class of acids are phosphorus-containing acids bearing an oleophilic hydrocarbon radical of between 12 and 25 carbon atoms, such as tetradecane-1-phosphinic acid, 3:5 di-isobutylbenzene phosphinic acid, methylhexyl-decane-1-phosphinic acid, dodecane 1-phosphonic acid, 10-phenyldecane-1-phosphonic acid, 10-phenyldecane-1-phosphonic acid and 2:4-diamyl cyclohexane phosphonic acid.  The anionic surface-active agents may be salts or partial esters of the above acids, especially salts of the acids with water-soluble amines of low molecular weight.  The compositions generally contain 25 to 100 per cent by weight of the gelling agent of both the cationic and anionic surface-active agents, preferably from 35 to 65 per cent. Specification 695,309 is referred to.