Patent GB-842263-A (GB)
Title: Process for the preparation of perhydrate compounds containing water of crystallisation
IPC: C01B15/00
Filed: 1957-01-18
Abstract: Washing and bleaching compositions contain perhydrates having water of crystallization which have been prepared by reacting hydrogen peroxide and water with an inorganic salt, such as a phosphate, carbonate, silicate, borate, or sulphate of an alkali or alkaline earth metal, in the presence of an inert organic liquid (see Group III).  Stabilizers such as tetrasodium pyrophosphate, potassium pyrophosphate, sodium or potassium silicate, stannous chloride, magnesium silicate, orthohydroxyquinoline, or pyridine carboxylic acids such as trimesitic or nicotinic acids may be employed.  The compositions may also contain surface-active substances such as alkyl-benzene sulphonates, alkyl sulphates and fatty alcohol sulphates with 10 to 20 carbon atoms, and condensation products of ethylene oxide with fatty acids, fatty alcohols and phenols which contain 4 to 24 ethylene oxide groups per molecule.  Soap or mixtures with the above synthetic surfactants may also be employed, and the compositions may also contain neutral salts such as sodium or magnesium sulphate, sodium carbonate or bicarbonate and di- or tri-sodium phosphates, pyro and polyphosphates, particularly hexametaphosphates, together with dyestuffs and optical brighteners. According to examples, (3) a bleaching composition consists of sodium tripolyphosphate peroxypentahydrate and 0.5 part of magnesium silicate or 0,1 part of nicotinic acid.  (20) A washing composition, for treatment of silk and artificial fibres at reduced temperatures, consists of a C12 fatty alcohol sulphonate, a C12 alkylbenzene sulphonate, sodium tripolyphosphate, magnesium silicate, sodium sulphate, optical brighteners, foam stabilizers, thread-protecting agents and dyestuffs, and disodium phosphate perhydrate of formula Na2HPO4,8H20 1,5 H202.ALSO:Perhydrates containing water of crystallisation, especially suitable as components of washing or bleaching compositions, are prepared by reacting, in the presence of an inert organic liquid, hydrogen peroxide, water and an inorganic salt which is capable of binding water of crystallisation; alternatively, starting materials equivalent to these reactants may be employed.  The reactants are provided in a proportion corresponding to the formula A. x H2O . y H2O2 where A is the inorganic salt and x and y are terms in the series 1, 1 1/2 , 2, 2 1/2 , 3 &c., and the sum of x and y is not greater than the number of moles of water of crystallization which the inorganic salt is capable of binding.  The invention is particularly directed to the preparation of perhydrates of alkali and alkaline-earth metal salts of phosphoric, carbonic, silicic, boric and sulphuric acids.  The inorganic salts are preferably anhydrous or contain only part of the water of crystallization. Suitable inert organic liquids are carbon tetrachloride, chloroform, decahydronaphthalene, benzene, toluene, xylene, petrol, hexachlorobenzene, chlorinated hydrocarbons such as trichloroethane and tetrachloroethane or a petrol ether.  The reaction may be effected at 0 to 55 DEG C. and the reaction product is separated by crystallizing or filtration.  Some of the water in the reaction product may be removed by careful dehydration without losing the hydrogen peroxide.  According to examples (1) sodium tripolyphosphate was dispersed in carbon tetrachloride and treated at room temperature with an aqueous solution of hydrogen peroxide; crystalline sodium tripolyphosphate perhydrate was obtained. Chloroform may be used in place of carbon tetrachloride.  (5) Anhydrous trisodium ortho phosphate was suspended in chloroform and reacted with an aqueous solution of hydrogen peroxide at 15 to 20 DEG C. and a reaction product corresponding to Na2PO2.2H2O was recovered. Sodium or potassium ortho phosphate perhydrates of varying compositions may be similarly prepared.  (7) Six of the eight moles of water of crystallization in the phosphate of example 5 may be removed by heating at 35 to 40 DEG C. in vacuo.  (8) Disodium phosphate dihydrate and caustic soda were suspended in chloroform and treated at 10 DEG C. with an aqueous solution of hydrogen peroxide, to obtain trisodium phosphate-octahydrate-monoperhydrate.  (11) Sodium metasilicate monohydrate was suspended in chloroform and aqueous hydrogen peroxide added thereto at 30 to 40 DEG C. with stirring; a tetrahydrated metasilicate monoperhydrate was obtained. The relative proportions of water of crystallization and hydrogen peroxide in the product may be varied by varying the starting material proportions.  (12) Anhydrous sodium carbonate was suspended in carbon tetrachloride or chloroform and aqueous hydrogen peroxide added at 10 DEG C. to obtain the monoperhydrate nonahydrate; various other percarbonates may be obtained by altering the proportions. (13) Chloroform was mixed with water and the mixture cooled to -10 DEG C. and stirred with ground sodium peroxide; carbon dioxide was passed in at 0-5 DEG C. with stirring and a crystalline sodium carbonate perhydrate-9-hydrate was obtained. (14) Sodium borate perhydrate-5-hydrate was obtained by reacting borax suspended in carbon tetrachloride with aqueous hydrogen peroxide.  (15) Anhydrous sodium sulphate was suspended in benzene and reacted at 10 DEG C. with aqueous hydrogen peroxide to obtain a sodium sulphate mono perhydrate-6-hydrate.  (16) Sodium peroxide was suspended in chloroform at 0 DEG C. and treated with sulphuric acid to obtain sodium sulphate - hexahydrate - monoperhydrate. (17) Anhydrous magnesium carbonate was suspended in petrol ether and an aqueous hydrogen peroxide solution added at 20 DEG C.  A magnesium carbonate perhydrate tetrahydrate was obtained.  The perhydrates may be employed as bleaching, washing or penetrating agents and may be stabilized with tetra-sodium pyrophosphate, potassium pyrophosphate, sodium or potassium silicate, stannous chloride, magnesium silicate, orthohydroxyquinoline or pyridine carboxylic acids such as trimesitic acid or nicotinic acid.  Surface-active substances such as alkylbenzene sulphonates, alkyl sulphates and fatty alcohol sulphates with 10 to 20 carbon atoms, and condensation products of ethylene oxide with fatty acids, fatty alcohols and phenols which contain 4 to 24 ethylene oxide groups per molecule, may be employed.  Soap or mixtures with the above synthetic surfactants may also be employed and the washing compositions may also contain neutral salts such as sodium or magnesium sulphate, sodium carbonate or bi-carbonate and di- or tri-sodium phosphates, pyro- and poly-phosphates, particularly hexametaphosphates, together with dyestuffs and optical brightners. According to examples (2) a washing composition containing pyrophosphate, sodium sulphate, water - glass, magnesium silicate and a fatty alcohol sulphate is spray-dried and mixed with sodium tripolyphosphate peroxide pentahydrate: the magnesium silicate may be replaced by orthohydroxyquinoline, and an improved washing composition is obtained if the sodium tripolyphosphate perhydrate is replaced by perborate.  (3) A bleaching composition consists of sodium tripolyphosphate peroxypentahydrate and 0.5 part of magnesium silicate or 0.1 part of nicotinic acid.  (4) A penetrating and rinsing composition consists of sodium tripolyphosphate peroxypentahydrate, waterglass, magnesium silicate and fatty alcohol sulphate.  (18) A sodium pyrophosphate perhydrate of formula Na4P2O7 . 3H2O2 is mixed with minor amounts of waterglass, ortho-hydroxyquinoline and fatty alcohol sulphonates.  (19) A product particularly suitable for cleaning and disinfecting food containers, such as milk bottles, consists of an alkali metal silicate having a molar ratio SiO2 : Na2O of 3.5:1, a fatty alcohol sulphonate, sodium tripolyphosphate and trisodium phosphate-perhydrate of formula Na3PO4 . 8H2O . H2O2.  (20) A washing composition, for treatment of silk and artificial fibres at reduced temperatures, consists of a C12 fatty alcohol sulphonate, a C12 alkylbenzene sulphonate, sodium tripolyphosphate, magnesium silicate, sodium sulphate, optical brighteners, foam stabilizers, thread protecting agents and dyestuffs, and disodium phosphate perhydrate of formula Na2HPO4 8H2O 1.5 H2O2. (21) An alkaline-reacting boiling washing composition (pH 10.5) is prepared by making a 1 % aqueous solution containing a fatty alcohol sulphonate, an alkyl benzene sulphonate, sodium pyrophosphate, tripolyphosphate, waterglass, sodium sulphate and sodium carbonate pentahydrate diperhydrate.  (22) A washing composition containing fatty alcohol sulphonate and alkylbenzene sulphonate, sodium pyrophosphate, alkali metal silicate, magnesium silicate and sodium sulphate is sprayed in paste like form and the dry product mixed with a sodium metaphosphate perhydrate of formula (NaPO3)3.2H2O . H2O2.  The metaphosphate perhydrate becomes hydrated in the washing bath and changes to tripolyphosphate.