Patent GB-1018344-A (GB)
Title: Cationic resin complexes,their production and uses
IPC: C14C9/00
Filed: 1964-05-11
Abstract: Leather, especially chrome leather, is retanned using as auxiliary tanning agent a water-soluble cationic resin which is prepared by reacting (a) an ammonium or amine salt of a carboxylic acid or an inorganic acid with formaldehyde, (b) the product from this with dicyandiamide, ammeline, a guanamine, guanidine or melamine, and then (c) this product with further formaldehyde (see Division C3). The cationic resin is used in conjunction with known anionic resins, especially those containing sulphonic acid groups in free or neutral salt form, e.g. sulphonated phenol, cresol, xylenol, naphthol, catechol, resorcinol, naphthalene or anthracene, or condensates with formaldehyde of sulphonated dicyandiamide, ammeline, a guanamine, guanidine or melamine, or condensates of urea-formaldehyde with sulphonated phenols.  The leather is soaked in an aqueous solution of either resin and is then treated with a solution of the other resin. Amounts of the cationic resin of the order of 5-15 weight per cent of the leather may be used.  In Examples VIII and VII, shaved chrome pretanned hides are treated with the reaction product of ammonium sulphate or ammonium borate, formaldehyde, dicyandiamide and further formaldehyde then with the reaction product of phenolsulphonic acid and a urea-formaldehyde condensate and are then fat-liquored with an agent comprising sulphated sperm oil, polyglycol oleate, the diethyl sulphate quaternary salt of oleic amide, and neatsfoot oil.ALSO:Cationic resin complexes are prepared by (A) reacting with formaldehyde an ammonium salt or an alkylmonoamine salt of a carboxylic acid or of a mineral acid, the amine salts containing at least one reactive hydrogen bound to each nitrogen, and the formaldehyde being sufficient to react with at least one hydrogen on each nitrogen in the salt, to form a methylolated amine salt; (B) reacting this with dicyandiamide, ammeline, guanidine, a guanamine or melamine, to give a complex salt;  and (C) reacting one molar proportion of this with at east one of formaldehyde.  In (A) suitable, amine salts are the chloride, formate, phosphate borate, sulphate, propionate, acetate, or butyrate of e.g. lauryl, ethyl, diethyl, propyl, methyl, ethanol, n-propanol, isopropanol, dioctyl, stearyl, dicapryl, methyl lauryl, and methyl soya amines, and suitable ammonium salts are the chloride, formate, phosphate, borate, sulphate, acetate or nitrate.  In (B) preferably 1-10 moles of methylolated amine salt are used per mole of amine base.  In (C) 1-10 moles of formaldehyde are preferably reacted with each mole of complex salt.  In Examples I-V condensates are prepared from 1 mol. boric acid/1 mol. NH4OH/1 mol. CH2O/1 mol. dicyandiamide/3 mols CH2O; 2 mols. boric acid/2 mols. NH4OH/4 mols. CH2O/2 mols. dicyandiamide/8 mols. CH2O; 2 mols. HCOONH4/2 mols CH2O/1 mol. dicyandiamide/2 mols. CH2O; 2 mols. hydroxyacetic acid/2 mols. NH4OH/2 mols. CH2O/2 mols. dicyandiamide/2 mols. CH2O; and 1 mol. (NH4)2SO4/2 mols. CH2O/1 mol. dicyandiamide/2 mols. CH2O.  Uses.-Precipitant for anionic surfactants and dispersants, hence coagulant for resin and rubber emulsions, and in the preparation of latex rubber, and beater additive in the treatment of cellulosic pulp with resins dispersed with anionic dispersants (see Division D2), and coagulant for systems using anionic surfactants and detergents (see Division C1); fillers for porous material e.g. leather, paper, fabrics; auxiliary tanning agent for use in conjunction with an anionic tanning agent (see Division C6); dyeing assistant for dyeing e.g. wool, silk, nylon, cotton, viscose rayon with acid dyes (see Division D1).ALSO:Waste water from systems using anionic surfactants and detergents is treated with a water-soluble cationic resin prepared by (A) reacting with formaldehyde an ammonium or amine salt of a carboxylic or inorganic acid; then (B) reacting the product with dicyandiamide, ammeline, a guanamine, guanidine or melamine; then (c) reacting this with more formaldehyde (see Division C3), which causes any residual anionic surfactant to coagulate. Specification 777,827 is referred to.ALSO:Water-soluble cationic resins which may be used as dyeing assistants or as beater additives for use in the treatment of cellulosic pulp are obtained by (A) reacting with formaldehyde an ammonium or amine salt of a carboxylic or inorganic acid, then (B) reacting the product with dicyandiamide, ammeline, a guanamine, guanidine, or melamine, and (C) reacting this with further formaldehyde.  (See Division C3).  As dyeing assistants the resins may be used for dyeing fibres of e.g. wool, silk, nylon, cotton, or viscose rayon with acid dyes.  As beater additives they may be used in conjunction with resins or polymers dispersed in water by means of anionic dispersants, which are coagulated by the cationic resins of the invention, so causing the polymer to be deposited uniformly upon the pulp.  In Example IX an ammonium borate/formaldehyde/dicyandiamide/formaldehyde condensate is used to precipitate an acrylonitrile latex on to a paper pulp in aqueous suspension.