Patent GB-785784-A (GB)
Title: Improvements in or relating to werner type complexes and compositions containing thesame
Inventor: DALTON RICHARD LEE
IPC: C03C25/38
Filed: 1954-02-08
Abstract: Solutions of Werner type complexes comprising a trivalent nuclear chromium atom co-ordinated with a carboxylic acido group having from 2 to 8 carbon atoms, the acido group being co-ordinated with the chromium atom through the carboxyl radical, are treated with a nitrogen base to adjust the pH of the solution to 4 to 7 thereby producing water-soluble polymerized Werner type complexes.  The nitrogen containing base may be ammonia, organic amines or a quaternary ammonium hydroxide.  The Werner complex is preferably methacrylato chromic chloride, but other acido groups may be used such as parahydroxybenzoate, acrylato, crotonato, sorbato, isocrotonato, alpha- and beta-ethylacrylato, angellato, tiglato, beta furyl-acrylato, cyanacetato, or chloroacetato.  The inorganic acid radical attached to the chromium may be the chloride, bromide or nitrate.  Specific examples of chromic chloride complexes contain as acido groups, para-aminobenzoato, benzoato, crotonato, cyanoacetato, 2,4-dihydroxybenzoato, furoato, gallato, glycinato, glyconato, nitrobenzoato, propionato, salicylato, thioglycolato, trichloroacetato and trimethylacetato.  The polymerized Werner complexes in aqueous solution may be employed as coupling agents between unsaturated resins and glass fibres and also to insolubilize polymers such as polyvinyl alcohol or polyvinyl acetate in the manufacture of sizes.  The size compositions may consist of polyvinyl acetate and the polymerized Werner complex together with a petroleum, vegetable or animal oil, a natural or synthetic wax or tristearin or water soluble amine acetate, starch or gelatine.  According to examples: (1) methacrylato chromic chloride was added to an aqueous solution of piperidine to adjust the pH to 5.9 and the solution of the polymerized Werner complex so obtained was employed to treat heat cleaned glass fabric, which after immersion in the solution was dried at 150 DEG  C.  The so-treated fabric was suitable for laminate preparation with a polyester resin.  (2) A methacrylato chromic chloride solution was treated with morpholine to adjust the pH to 5.68 and the resulting solution of polymerized Werner complex was used to treat glass fabric as in (1) above. Further examples (3) to (14) refer to the treatment of glass fabrics with solutions of Werner complexes which have been polymerized by treatment with ammonia, aniline, diethylene triamine, dimethylamine, N,N - dimethylethanolamine, N,N - dimethylethylene - diamine, ethanolamine, hexamethylenetetramine, pyridine, tetramethylammonium hydroxide, and trimethylamine.  (16) a sizing composition for glass fibres was prepared by mixing the methacrylato chromic chloride solution with one per cent ammonia solution to polymerize it and adding to the dilute polymerized methacrylato chromia solution, plasticised polyvinyl acetate and a small quantity of an amine acid lubricant such as octyl amino acetate.  Such a composition may be employed to size glass fibres by running them through the solution and drying at 125 DEG  C.  The polymerized Werner complexes may be employed to modify adhesive and film-forming compositions containing polyvinyl alcohol, polyvinyl acetate, alkyd resins and other synthetic gums and resins.  They also may be used as sizes for fibres, silver, yarns or fabrics of nylon, acrylic resins, polyesters, cellulose acetate, wool, cotton and ramie or mixtures thereof.ALSO:Basic chromic chloride having a basicity of 33.3 per cent is prepared by reducing chromic oxide with isopropanol in the presence of hydrochloric acid. Thus chromic oxide may be dissolved in 36 per cent hydrochloric acid and the solution added slowly to a refluxing solution of hydrochloric acid in isopropanol.  The resulting solution containing 8.35 per cent chloride and 7.43 per cent chromium was adjusted to a Cl: Cr ratio of 2: 1 by hydrochloric acid.ALSO:Solutions of Werner type complexes comprising a trivalent nuclear chromium atom coordinated with a carboxylic acido group having from 2 to 8 carbon atoms, the acido group being co-ordinated with the chromium atom through the carboxyl radical, are treated with a nitrogen base to adjust the pH of the solution to 4 to 7 thereby producing water-soluble polymerized Werner type complexes.  The nitrogen containing base may be ammonia, organic amines or quaternary ammonium hydroxides in which each organic constituent contains no carbon atoms further removed from the nitrogen atom than 4 and the total number of carbon atoms attached to the nitrogen exclusively through carbon is not more than twelve. There may, however, be more than twelve carbon atoms if they are not consecutive but are joined through other atoms such as oxygen, for example amines or quaternary ammonium bases substituted with polyethylene oxide groups.  The quaternary ammonium bases may have as substitutents aliphatic, alicyclic, aromatic or heterocyclic groups which may be the same or different; specifically the substituents may be tetramethyl, tetraethyl, tetra-isopropyl, tetra-n-propyl or combinations thereof and also dimethyldiallyl, tetraethanol, tri - methylethanol, phenyltrimethyl, trimethylcyclohexyl, N-methyl-pyridinium, N,N-dimethylpiperidinium and N,N-dimethylmorpholinium.  Specific amines are those containing as substituents mono-, di- or tri-ethyl, methyl, isopropyl, n-propyl or isobutyl; diethanolphenyl, mono - cyclopropyl, mono-, di- or tri-ethanolamine.  Cyclic amines such as pyridine, piperidine, morpholine, and pyrazine may be employed.  The Werner complex is preferably methacrylato chromic chloride but other acido groups may be used such as parahydroxy-benzoato, acrylato, crotonato, sorbato, isocrotonato, alpha- and beta-ethylacrylato, angellato, tiglato, beta furyl-acrylato, cyanacetato, or chloroacetato.  The inorganic acid radical attached to the chromium is preferably the chloride but the bromide or nitrate may be used.  Specific examples of chromic chloride complexes contain as acido groups, para-amino-benzoato, benzoato, crotonato, cyanoacetato, 2,4-dihydroxybenzoato, furoato, gallato, glycinato, gluconato, nitrobenzoato, propionato, salicylato, thioglycolato, trichloroacetato and trimethylacetato.  The ratio of chromium to acido groups in the initial Werner complex may be from 1 : 1 to 100 : 1 but is preferably between 2 : 1 and 5 : 1.  Werner type complexes having a low chromium ratio can be mixed with basic chromic chloride.  The polymerized Werner complexes in aqueous solution may be employed as coupling agents between unsaturated resins and glass fibres and also to insolubilize polymers such as polyvinyl alcohol or polyvinyl acetate in the manufacture of sizes. According to examples: (1) methacrylato chromic chloride was prepared by treating a basic chromium chloride solution with methacrylic acid and isopropanol which acted as a solvent.  The mixture was heated to reflux and allowed to cool, whereby methacrylato chromium chloride containing 6 per cent chromium was obtained in solution.  The solution was treated with a one per cent aqueous solution of piperidine to adjust the pH to 5.9 and a solution of the polymerized Werner complex was obtained.  (2) A methacrylato chromic chloride solution was polymerized by treatment with a one per cent solution of morpholine to adjust the pH to 5.68.  Further examples, (3) to (17) refer to solutions of Werner complexes which have been polymerized by treatment with ammonia, aniline, diethylene triamine, dimethylamine, N,N - dimethylethanolamine, N,N - dimethylethylene - diamine, ethanolamine, hexamethylenetetramine, pyridine, tetramethylammonium hydroxide, and trimethylamine.  The polymerized Werner complexes may be employed to modify adhesive and film-forming compositions containing polyvinyl alcohol, polyvinyl acetate, alkyd resins and other synthetic gums and resins.  They also may be used as sizes for fibres, sliver, yarns or fabrics of nylon, acrylic fibres, polyester fibres, cellulose acetate and natural fibres such as wool, cotton and ramie or mixtures thereof.