Patent GB-776156-A (GB)
Title: Improvements in or relating to werner type complexes and compositions containing thesame
IPC: C07F11/00
Filed: 1954-02-08
Abstract: A composition for treating glass fibres comprises an aqueous emulsion of polyvinyl acetate plasticized with dibutyl phthalate, a mixture of chromic chloride and polymeric methacrylato chromic chloride and an amine acetate lubricant, e.g. octylamine acetate.ALSO:Polymerized Werner complexes in which a trivalent nuclear chromium atom is co-ordinated with a carboxylic acido group of 2 to 8 carbon atoms, which complexes have a basicity of at least 70 per cent are obtained by treating aqueous solutions of Werner type acido chromic complexes in which the chromium is coordinated with a carboxylic acido group having 2 to 8 carbon atoms, with an anion exchanger, thereby polymerizing the Werner complex and reducing its basicity.  Suitable complexes are those containing chromium chloride having co-ordinated with the chromium the following acido groups: para hydroxybenzoato, para hydroxybenzophenoxy-acetato, acrylato, crotonato, sorbato, isoacrylato, angellato, tiglato, beta furyl-acrylato, cyanacetato and chloroacetato, furfurato, gallato, glycinato, gluconato, propionato, or salicylato together with substituent groups such as chloro, bromo, nitrato or hydroxyl, for example para aminobenzato, 2.4-dihydroxybenzato, nitro benzato, thioglycolato, trichloroacetato, trimethyl acetato.  The ratio of chromium to acido groups may be from 1:1 to 100:1, but preferably lies within the range of 2:1 to 5:1. Werner complexes having a low chromium ratio can be given an effectively higher ratio by the addition of basic chromic chloride before polymerization.  The polymerized Werner complexes and also the basic chromium chloride if present are converted on polymerization to a water-insoluble form.  Suitable anion exchangers are the metaphenylene diamine formaldehyde type or anion exchangers containing quaternary ammonium compounds or guanidine type anion exchangers.  The anion exchangers is first converted to basic form by treatment with an alkali and the polymerization of the Werner complex may be effected by simply adding the anion exchanger to an aqueous solution of the unpolymerized Werner complex or mixture thereof with a chromium salt.  The polymerized Werner complexes may be used for treating siliceous surfaces, especially glass fibres to render them abrasion resistant in which case they may be applied in the form of a colloidal solution and the treated material then dried at a temperature of at least 100 DEG  C.  The siliceous surfaces so treated form strong bonds with polyester and similar resins. Transparent or translucent polyester bonded glass fabrics or articles may be produced by impregnating glass fabric which has been treated with the Werner complexes with a polyester and forming a sandwich containing a plurality of such layers which is then cured to obtain laminated articles containing 65 to 55 per cent glass and from 35 to 45 per cent by weight of resin.  The polymerized Werner complexes may also be employed to form size compositions by admixture with polyvinyl acetate.  Such compositions may contain a lubricant such as petroleum, vegetable or animal oil, a natural or synthetic wax or lubricants such as amine acetates.  The sizes may also contain starch or gelatine.  The amount of polymerized Werner complex employed may be from 2 to 25 per cent of the polyvinyl acetate.  According to examples: (1) methacrylato chromic chloride was prepared from basic chromic chloride by adding methacrylic acid and isopropanol to a basic chromic chloride solution having a chlorine to chromium atomic ratio of 2:1.  The mixture was refluxed and after cooling the methacrylato chromic chloride contained 6 per cent chromium and was soluble and had a chloride to chromium ratio of 2:1.  The methacrylato chromic chloride so prepared was diluted with water and treated with the basic form of an amminated phenol-formaldehyde resin to produce a polymerized Werner complex in colloidal form having a basicity of 83.3 per cent.  The polymerized complex was employed to treat the glass fabric by immersion followed by drying at 150 DEG  C. (3) 2,4-dihydroxybenzoato chromic chloride was treated as in Example 1 and the polymerized complex employed to treat glass fibres.  (4) Methacrylato chromic chloride was treated with an amminated phenol-formaldehyde resin as in (1) above and after filtration the filtrate containing the polymerized Werner complex having a basicity of 83.3 was mixed with plasticised polyvinyl acetate emulsion containing a minor amount of amine acetate lubricant. This composition was applied to glass fibres by immersion after which the fibres were dried at 125 DEG  C.  (6) A polyvinyl acetate emulsion containing 55 per cent solids was plasticised with dibutyl phthalate and mixed with the polymerized Werner complex and octyl amine acetate lubricant.  The composition was applied to glass fibres by immersion followed by drying at 125 DEG  C.  The treated fibres were employed for reinforcing plastic materials.ALSO:Polymerized Werner complexes in which a trivalent nuclear chromium atom is coordinated with a carboxylic acido group of 2 to 8 carbon atoms, which complexes have a basicity as defined in the Specification of at least 70 per cent, are obtained by treating aqueous solutions of Werner type acido chromic complexes, in which the chromium is co-ordinated with a carboxylic acido group having 2 to 8 carbon atoms, with an anin exchanger, thereby polymerizing the Werner complex and reducing its basicity. The complex may be used for sizing glass fibres.  Suitable complexes are those containing chromium chloride having, co-ordinated with the chromium, the following acido groups:- parahydroxybenzoato, parahydroxybenzophenoxy-acetato acrylato, crotonato, sorbato, isoacrylato, angellato, tiglato, beta furyl-acrylato, cyanacetato and chloracetato, furfurato, gallato, glycinato, gluconato, propionato, or salicylato, with or without substituent atoms or groups such as chloro, bromo, nitrato or hydroxyl, for example para-aminobenzato, 2.4-dihydroxybenzato, nitrobenzato, thioglycolato, trichloracetato and trimethyl acetato.  The ratio of chromium to acido groups may be from 1:1 to 100:1 but preferably lies within the range of 2:1 to 5:1. Werner complexes having a low chromium ratio can be given an effectively higher ratio by the addition of basic chromic chloride before polymerization.  The polymerized Werner complexes and also the basic chromium chloride if present are converted on polymerization to a water-insoluble form.  Suitable anion exchangers are of the metaphenylene diamine formaldehyde type, anion exchangers containing quaternary ammonium compounds of guanidine type anion exchangers. The anion exchanger is first converted to basic form by treatment with an alkali and the polymerization of the Werner complex may be effected by simply adding the anion exchanger to an aqueous solution of the unpolymerized Werner complex or mixture thereof with a chromium salt.  The polymerized Werner complexes may be applied to glass fibres in admixture with polyvinyl acetate in the form of a colloidal solution and the treated material is then dried at a temperature of at least 100 DEG C.  The siliceous surfaces so treated are abrasion-resistant and form strong bonds with polyester and similar resins.  Such compositions may contain a lubricant such as petroleum, a vegetable or animal oil, a natural or synthetic wax, an amine acetate, starch or gelatine.  The amount of polymerized Werner complex employed may be from 2 to 25 per cent of the polyvinyl acetate.  According to examples, (1) methacrylato chromic chloride is diluted with water and treated with the basic form of an aminated phenol-formaldehyde resin to produce a polymerized Werner complex in colloidal form having a basicity of 83.3 per cent.  The polymerized complex is employed to treat glass fabric by immersion, followed by drying at 150 DEG C. (3) 2.2-Dihydroxybenzoato chromic chloride is treated as in Example 1 and the polymerized complex employed to treat glass fibres.  (4) Methacrylato chromic chloride is treated with an aminated phenol-formaldehyde resin as in (1) and, after filtration, the filtrate containing the polymerized Werner complex having a basicity of 83.3 per cent is mixed with plasticized polyvinyl acetate emulsion containing a minor amount of amine acetate lubricant.  This composition is applied to glass fibres by immersion, after which the fibres are dried at 125 DEG  C. (6) A polyvinyl acetate emulsion containing 55 per cent solids is plasticized with dibutyl phthalate and mixed with the polymerized Werner complex and octyl amine acetate lubricant.  The composition is applied to glass fibres by immersion, followed by drying at 125 DEG C.  The treated fibres are employed for reinforcing plastic materials.ALSO:Basic chromic chloride is prepared by reducing a hydrochloric acid solution of chromic oxide with isopropanol.  Then a solution of 33.6 parts of chromic oxide in 66.4 parts of 36 per cent hydrochloric acid were slowly added to a refluxing solution of 5.4 parts of hydrochloric acid in isopropanol. The resulting solution analysed 8.35 per cent chloride and 7.43 per cent chromium.  The chlorine/chromium atomic ratio was adjusted to 2:1 with 4.92 parts of hydrochloric acid to produce a basic chromic chloride having a voscity of 33- 1/3 per cent.