Patent GB-748391-A (GB)
Title: Fabrications of glass fibres and method for the production thereof
Inventor: STEINMAN ROBERT
IPC: C03C25/38
Filed: 1951-05-04
Abstract: An impregnating composition for coating the glass fibre in a textile fabric contains polyvinyl chloride, di-octyl phthalate, a chromium complex obtained from chromic chloride and 1-cyano propionic acid, and water.  The chromium complex is incorporated in an emulsion or dispersion of the other compounds prepared with a cationic emulsifier.  The composition may be applied by knife coating and the product heated at 250-350 DEG  F.  Reference has been directed by the Comptroller to Specification 712,784, [Group IV (b)].ALSO:Werner type complexes wherein a chromium nuclear atom is co-ordinated with a saturated carboxylic acido group having up to seven carbon atoms in aliphatic arrangement and constituted with a grouping having a labile hydrogen atom attached to a carbon atom, a polar substituent group or a hydrogen atom attached to the same carbon atom as a highly negative group or to a carbon atom in a -position relative thereto are prepared by reacting a solution of a basic chromium salt with the carboxylic acid as described in U.S.A. Specifications 2,273,040 and 2,356,161.  Thus, a solution of CrO3 in hydrochloric acid is refluxed with isopropanol to give a basic chromic chloride which is heated with the acid. Acids specified are those containing halogen substituents, namely mono- and dichloracetic, a -brom- and a ,b -dichlor-propionic; those containing a cyano group of formul <FORM:0748391/IV(a)/1> where R1 is hydrogen or a monovalent alkyl, aryl, aralkyl or heterocyclic radical or derivative thereof having up to seven carbon atoms in aliphatic arrangement and R2 is a like divalent radical; and those having active methylene groups as in malonic.  Examples refer to complexes of chromic chloride with cyanoacetic, dichloracetic, and 1 - cyanopropionic acids. Specification 11111/47 as open to inspection under Sect. 91, also is referred to.  Reference has been directed by the Comptroller to Specification 712,784.ALSO:The surfaces of glass fibres are treated with a Werner type complex wherein a chromium nuclear atom is co-ordinated with a saturated carboxylic acido group having up to seven carbon atoms in aliphatic arrangement and containing a grouping having (1) a labile hydrogen atom attached to a carbon atom, or (2) a polar substituent atom or group, or (3) a hydrogen atom attached to the same carbon atom as a highly negative atom or group or to a carbon atom in a -position relative thereto.  The fibres may thereby be made to adhere to coating materials, or their hydrophilic or hydrophobic properties may be improved.  The complexes may be prepared as described in U.S.A.  Specifications 2,273,040 and 2,356,161.  Thus, a basic chromium salt is made by reducing chromium trioxide with isopropanol in hydrochloric acid, and the carboxylic acid is then added with isopropanol.  If the acido group contains a labile hydrogen atom, the glass fibres coated with the complex are more attractive to materials having an atom of oxygen, nitrogen or sulphur.  Alternatively, if the acido group contains such atoms in, e.g., ether, ester, ketone, aldehyde, alcohol, nitro, cyano, azo, amino or amido groups or their thio modifications, or nitrogen in a heterocyclic ring, the glass is more receptive to materials containing labile hydrogen. When the acido group has a polar substituent, the coated surface is readily wetted by materials having a polar atom or group, while a non-polar acido group gives a surface readily wetted by non-polar materials.  Highly negative atoms or groups which may be present to activate the hydrogen atom include halogen atoms and cyano, nitro, and active methylene groups as present, for example, in mono-and dichloracetic acid, a -brom-and a , b -dichlorpropionic acid, and malonic acid.  Other such groups are aryl and carbonyl groups. Polar atoms or groups include halogen atoms and keto, cyano, nitro, nitroso, phenyl, carboxy, hydroxy, amino and ester groups.  The chromium complex may be applied to the fibres as a 0.1 - 10 per cent solution, preferably as a 0.2 - 2 per cent solution, in water alcohol.  It may be applied while forming the fibres or afterwards, and is insolubilized by air-drying or by heating for 1-30 minutes at 150-300 DEG F.  The complex may also be applied with waxes, oils, varnishes and the like, e.g. with a size. The treated fibres may be coated with synthetic resins to make plastics, coated fabrics, laminates and electrical insulation, and dyes or pigments, metal powders or flakes may also be applied. They may be used as a contact medium in the separation of different materials where one preferentially wets the fibres, e.g. in rectifying alcohol - water mixtures or coalescing a water-in-oil emulsion.  In examples, (1) a chromic chloride cyanoacetic complex is used to treat a fabric of glass fibres after heating to burn off the size, the dried or heated fabric then being impregnated with resins of the polystyrene, polyvinyl chloride or synthetic rubber types; (2) continuous glass filaments in the form of strands or yarns are wiped with a size containing a dichloracetic acid complex, dextrinized starch, gelatin and polyvinyl alcohol in water; (3) a resinous impregnating composition for a glass fabric contains polyvinyl chloride, dioctyl phthalate and a 1-cyanopropionic acid complex. Specification 11111/47 as open to inspection under Sect. 91 also is referred to.  Reference has been directed by the Comptroller to Specification 712,784.ALSO:Werner type complexes wherein a chromium atom is co-ordinated with a saturated carboxylic acids group having up to seven carbon atoms in aliphatic arrangement and constituted with a grouping having a labile hydrogen atom attached to a carbon, a polar substituted group or a hydrogen atom attached to the same carbon atom as a highly negative group or to a carbon atom in a position relative thereto are used to coat glass fibres which are present as a contact medium in rectifying alcohol-water mixtures. Reference has been directed by the Comptroller to Specification 712,784.ALSO:The surfaces of glass fibres are treated with a Werner type complex wherein a chromium nuclear atom is co-ordinated with a saturated carboxylic acido group having up to seven carbon atoms in aliphatic arrangement and constituted with a grouping having a labile hydrogen atom attached to a carbon atom, a polar substituent group or a hydrogen atom attached to the same carbon atom as a highly negative group or to a carbon atom in a  position relative thereto.  The fibres may thereby be made to adhere to coating materials or their hydrophilic or hydrophobic properties may be improved.  If the acido group contains a labile hydrogen atom, the glass fibres coated with the complex are more attractive to materials having an atom of O, N or S. Alternatively, if the acido group contains such atoms, e.g. in ether, ester, ketone, aldehyde, alcohol, nitro, cyano, azo, amino or amido groups or thio modifications or nitrogen in a heterocyclic ring, the glass is more receptive to materials containing labile hydrogen.  Where the acido group has a polar substituent, the coated surface is readily wetted by materials having a polar atom or group, while a non-polar acido group gives a surface readily wetted by non-polar materials.  Highly negative groups which may be present to activate the hydrogen atom include halogens, cyano, nitro, and active methylene groups as present, for example, in mono- and dichloracetic acid, a  - brom - and a , b  - dichlor - propionic acid, and malonic acid.  Other such groups are aryl and carbonyl.  Polar groups include halogeno, keto, cyano, nitro, nitroso, phenyl, carboxy, hydroxy, amine and ester type groups.  The chromium complex may be applied to the fibres as a 0.1-10 per cent solution preferably as a 0.2-2 per cent solution in water-alcohol.  It may be applied while forming the fibres or afterwards, and is insolubilized by air drying or by heating for 1-30 minutes at 150-300 DEG F.  In examples: (1) a mixture of chromic chloride-cyanoacetic acid complex isopropyl alcohol and water is used to treat a fabric of glass fibres; (2) continuous glass filaments in the form of strands or yarns are wiped with a size containing a chromic chloride-dichloracetic-acid complex, dextrinized starch, gelatine and polyvinyl alcohol in water; (3) a resinous impregnating composition for a glass fabric contains water, polyvinyl chloride, dioctyl phthalate, and a chromic chloride-1-cyanopropionic acid complex.  Specification 11,111/47 open to inspection under Sect. 91, is referred to.  Reference has been directed by the Comptroller to Specification 712,784 [Group IV(b)]