Patent GB-442466-A (GB)
Title: A process for the preparation of aqueous emulsions
IPC: C09K23/00
Filed: 1935-01-14
Abstract: Stable aqueous emulsions useful as cold wetting-agents are obtained by reacting two colloidal electrolytes, one of which possesses a colloidal anion while the other possesses a colloidal cation and is a quaternary heterocyclic ammonium salt having a "high molecular" aliphatic substituent and does not contain an aromatic ring, the electrolytes being reacted in electro-equivalent quantities, to form a water-insoluble electro-neutral compound, and a small quantity of one of the components of the electro-neutral compound or other colloidal electrolyte being then added so that an emulsion is formed. The colloidal electrolyte added to form the emulsion may be added to the electro-neutral compound, or may be present during its formation, and an additional inert fatty substance may also be added, either to the electro-neutral compound or to one or both of its components before mixing.  Suitable electrolytes having colloidal cations are alkyl and alkylene pyridinium salts, and the corresponding compounds of pyridine derivatives and substitution products, and those having colloidal anions include alkyl esters of polybasic strong mineral acids, e.g. dodecyl, hexadecyl, octadecenyl and octadecyl sulphuric acids or alkali salts; fatty acids and alkali salts thereof; turkey red oils; or naphthalene and benzene compounds, having one or more carboxyl, sulphonic or sulphate groups.  According to examples: (1) paraffin oil or soft paraffin is emulsified in the cold with the alkali salt of dodecyl acid ester, and lauryl pyridinium bisulphate is added until the paste attains maximum viscosity; the brine can be separated, and the electro-neutral compound, which occludes the paraffin, can be converted into a positively charged emulsion by further addition of lauryl pyridinium bisulphate or into a negatively charged emulsion by the addition of dodecyl sulphuric acid ester; (2) oleic acid is stirred in the cold with lauryl pyridinium bisulphate to form a jelly, which readily forms a positively charged emulsion with water; (3) Marseilles soap is dissolved in hot water to which lauryl pyridinium bisulphate is added; the mass is boiled and stirred until the electro-neutral compound separates out; oleic acid may also be used; the product is stirred in the cold with train oil, and a further addition of 1--5 per cent of alkyl pyridinium salt is made to give a stable emulsion; (4) the reaction product of Marseilles soap and lauryl pyridinium bisulphate as obtained in the previous example is stirred with lecithin, and lauryl pyridinium bisulphate is added; the product gives stable emulsions with water; (5) mineral oil is stirred in the cold with lauryl pyridinium chloride, the product according to example 3 is added, and finally lauryl pyridinium bisulphate; (6) octadecyl sulphuric acid and lauryl pyridinium bisulphate are reacted, giving an insoluble electro-neutral compound, which can be emulsified with fatty alcohol sulphonates and turkey red oils to give negatively charged emulsions; cation-active agents give positively charged emulsions; (7) neat's-foot oil is stirred with the electro-neutral compound obtained from sodium b -naphthol sulphonate and lauryl pyridinium bisulphate, and the mass is treated with lauryl pyridinium bisulphate; (8) mineral oil is heated, sulphonated castor oil added and lauryl pyridinium bisulphate, are added in turn, and finally lauryl pyridinium bisulphate is added.  The emulsions thus obtained find application in the textile, leather, and paper industries.  They are particularly useful as cold wetting agents when relatively large amounts of unsaturated fatty alcohol sulphonates or the benzene or naphthalene derivatives mentioned above are employed.ALSO:Stable aqueous emulsions are obtained by reacting two colloidal electrolytes, one of which possesses a colloidal anion and, the other a colloidal cation and is a quaternary heterocyclic ammonium salt having a high molecular aliphatic substituent and does not p  contain an aromatic ring, in electro-equivalent quantities to form a water-insoluble electro-neutral compound and adding a small quantity of one of the components of the electro-neutral compound or other colloidal electrolyte so that an emulsion is formed.  The colloidal electrolyte added to form the emulsion may be added to the electro-neutral compound, or may be present during its formation, and an additional inert fatty substance may also be added, either to the electro-neutral compound or to one or both of its components before mixing.  Suitable electrolytes having colloidal cations are alkyl and alkylene pyridinium salts and the corresponding compounds of pyridine derivatives and substitution products, and those having colloidal anions include alkyl esters of polybasic strong mineral acids, e.g. dodecyl, hexadecyl, octadecenyl and octadecyl sulphuric acids or alkali salts; fatty acids and alkali salts thereof; turkey red oils; or naphthalene and benzene compounds having one or more carboxyl, sulphonic or sulphate groups.  According to examples: (1) 700 gms. of paraffin oil or soft paraffin are emulsified in the cold with 140 gms. of the alkali salt of dodecyl-sulphuric acid ester.  40 per cent lauryl pyridinium bisulphate is added until the paste attains maximum viscosity.  The brine can be separated by heating and the electro-neutral compound, which occludes the paraffin, can be converted into a positively charged emulsion by further addition of lauryl pyridium bisulphate or into a negatively charged emulsion by the addition of dodecyl sulphuric acid ester.  (2) 60 gms. of oleic acid are stirred in the cold with 450 gms. of 40 per cent lauryl pyridinium bisulphate to form a glassy jelly, which readily forms a positively charged emulsion with water.  (3) 3000 gms. Marseilles soap (fat content 84 per cent) are dissolved in hot water to which is rapidly added 3000 gms. of 40 per cent lauryl pyridinium bisulphate. The mass is boiled and stirred until the foam subsides and the electro-neutral compound separates out as a black-green mass which is insoluble in hot and cold water.  The aqueous phase is separated as hot as possible. Products of lighter colour are obtained with oleic acid. 150 gms. of this product are stirred in the cold with 850 gms. of train oil.  A further addition of 1--5 per cent of alkyl hydridinium salt gives a stable emulsion of train oil with cold water.  (4) 20 gms. of the reaction product of Marseilles soap and lauryl pyridinium bisulphate as obtained in the previous example are stirred with 80 gms. of lecithin, 100 gms. of 40 per cent lauryl pyridinium bisulphate are added.  The product is a dark, clear oil giving stable emulsions with water.  (5) 50 gms. mineral oil are stirred in the cold with 50 gms. lauryl pyridinium chloride.  50 gms of the product according to example 3, are added, and finally 45 gms. of lauryl pyridinium bisulphate.  (6) 600 gms. of octadecyl sulphuric acid (about 80 per cent) and 1000 gms. of 40 per cent lauryl pyridinium bisulphate are reacted, giving an insoluble, sticky electro-neutral compound, which can be emulsified with fatty alcohol sulphonates and turkey red oils to give negatively charged emulsions. Cation-active agents give positively charged emulsions.  (7) 400 gms. neat's-foot oil are stirred with 40 gms. of the electro-neutral compound obtained from sodium b -naphthol sulphonate and lauryl pyridinium bisulphate. The mass is treated with 120 gms. of 40 per cent lauryl pyridinium bisulphate.  (8) 200 gms. of mineral oil are heated, 30 gms. of sulphonated castor oil added and finally 70 gms. of 60 per cent lauryl pyridinium bisulphate, with constant stirring. When cool, 60 gms. of 60 per cent lauryl pyridinium bisulphate are added. The emulsions thus obtained find application in the textile, leather, and paper industries, e.g. as lubricating agents, spinning fats, &c.  They may also be used as cold wetting agents, especially when relatively large amounts of unsaturated fatty alcohol sulphonates or the benzene or napthalene derivatives mentioned above are employed for rendering soluble, in which case no foreign fat is added to the components of the electro-neutral compound.  The emulsions may also be used for the greasing of leather, especially if the electro-neutral compounds contain known leather fats and oils and emulsification is effected with substances having surface active cations.  They can be used in the cold, and avoid subsequent darkening of the leather, and are also resistant to calcium ahd chromium salts and acids; de-acidifying of the leather being unnecessary.