Patent GB-788151-A (GB)
Title: Solid siliceous materials of high surface area, methods of making the same, and compositions containing them
Inventor: ILER RALPH KINGSLEY
IPC: G03C1/95
Filed: 1953-10-19
Abstract: Surface-esterified siliceous material (see Group III) may be incorporated into textile products at any stage in their manufacture from separate fibres to the finished product which may be a knitted, woven, felted, resin-bonded or pile fabric.  Fibres specified are synthetic and glass fibres, wool, cotton, silk, ramie, hemp, alpaca, camel hair, fur, feathers, goat hair and horse hair.  The surface-esterified material is prepared by chemically bonding -OR groups, where R is a hydrocarbon group other than aryl, directly to the silicon atoms of the surface, the silica having specified dimensions greater than colloidal.  The material may be applied to the surface of fibres immediately after spinning as a suspension in a liquid or as a powder.  It is preferably incorporated into the sizing agent applied during spinning and weaving.  It may also be incorporated in a binding agent which acts as an adhesive and setting agent when heat is applied.  The material may also be used together with colloidal inorganic binders, e.g. aluminium phosphate, in the production of glass fibre mat products for use as gas or air filters or battery separators.  The material may also be incorporated in creaseproofing, crushproofing and slip proofing agents for textiles comprising, e.g., rubber, urea-formaldehyde, melamine-formaldehyde, or phenol formaldehyde resins, polyvinyl alcohol, polyvinyl acetate and cellulose acetate.  The material may also be incorporated is softening, anti-static and delustreing agents comprising, e.g., stearyl trimethylammonium bromide.  The material may also be incorporated into normally hydrophobic textiles to improve water absorption.  The fibres may be heated, or small amounts of water-insoluble adhesive may be used to anchor the material.  The material may also be incorporated into nylon and acrylonitrile. Highly esterified silica renders the surface of woven textiles hydrophobic when applied thereto as a fine dust, especially when combined with anhydrophobic binder.  It may be used in water-repellent finishes for textiles comprising, e.g., an aqueous dispersion of paraffin wax, carnauba, beeswax, silicone oil or resin. Glass fibres may be coated with silica, by treating sodium silicate solution with an acid in the presence of the fibres, and the silica may thereafter be surface esterified.  The surface-esterified material may be incorporated in mordants for textiles, including glass fibre products, to produce a better bond or merely as an anti-caking or dispersing agent or extender.  Soluble dyes may be applied to the surface of the siliceous material by absorption from an aqueous or organic solvent solution.  Insoluble dyes may also be deposited on the siliceous material.  The siliceous material may also be incorporated into paste dyes which are applied to fabrics by means of rollers.  Specification 788,152, [Group III], is referred to.ALSO:Non-colloidal hydrophilic siliceous material having a minimum aggregate diameter of 150 millimicrons and a specific surface area of at least 1 sq. m/gm. is subjected to surface esterification to produce a product which is organophilic (having about 100 ester groups per 100 sq. millimicrons of surface) or both organophilic and hydrophobic (having about 200 ester groups per 100 sq. millimicrons of surface).  The siliceous substrate material preferably has a specific surface area of 200-900 sq. m/gm. more preferably 200-400 sq. m/gm., and is preferably the friable dehydrated silica gel described in Specification 788,152.  The substrate may also consist of a silica aerogel or of clay, glass fibres or titania having a coating of silica.  Wet substrates may be dried before treatment, either directly or by first replacing the water by a solvent such as acetone.  Water may also be removed by azeotropic distillation with methyl ethyl ketone, n-butyl alcohol, or kerosene or with the alcohol subsequently to be used as esterifying agent.  Surface esterification may be carried out at a temperature above 100 DEG  C. with a primary or secondary alcohol containing up to 18 carbon atoms.  Alcohols specified are methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec.-butanol, n-pentanol, iso-pentanol, 2-pentanol, n-hexanol, 4-methyl-2-pentanol, n-heptanol, 2-4-dimethyl-3-pentanol, n-octanol, 2-octanol, n-nonanol, 2,2,4-trimethyl-1-hexanol, n-decanol, n-undecanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, 5,7,7 - trimethyl - 2 - (1,3,3 - trimethyl butyl)-1-octanol, cyclopentanol, cyclohexanol, cycloheptanol, menthol, allyl alcohol, crotyl alcohol, oleyl alcohol, citronellol, geraniol, propargyl alcohol, 2-phenylethanol, hydrocinnamyl alcohol, alpha methylbenzyl alcohol and cinnamyl alcohol.  The water content of the reaction mass may be maintained below 5 per cent, preferably below 3 per cent, and for maximum esterification below 1.5 per cent. Reaction may be carried out with up to 30 per cent of water at a temperature of 270-375 DEG  C., a pressure of 2000-20,000 lb/sq. in. and a pH of 4.5-7.5, the pressure being vented while maintaining the temperature above the critical temperature and the product being cooled in the substantial absence of air.  The esterifying alcohol may be removed by vaporization or by extracting with a low-boiling solvent such as methyl ethyl ketone, chloroform or ether. Surface-esterified silica may be compressed and sintered, preferably with a binder, e.g. one which burns out on sintering or aluminium acetate or a metal stearate.  Beads of silica gel may be produced by forming a dispersion of a surface esterified silica in kerosene, adding ethyl silicate and dispersing the mixture in strong sulphuric acid.  A catalyst comprising siliceous material having a metal coating is prepared by incorporating a metal oxide with the surface-esterified siliceous material and then heating in an inert atmosphere.  The metal oxide may be admixed with or deposited on the surface esterified siliceous material. Surface-esterified siliceous material may be mixed with aluminium chloride and formed into catalyst pellets.  Fuel oil for diesel engines and alcohol for rocket motors may contain a dispersion of the surface esterifier siliceous material, in which may be incorporated chromium oxide.  Liquid and dry lubricants and greases may comprise the surface-esterified siliceous material.  Liquid lubricant constituents specified are kerosene, gasoline, naphtha, benzene and carbon tetrachloride. Solid lubricants specified are graphite, molybdenum sulphide, tale and mica.  Greases may comprise petroleum oil, stearic acid, di (2-ethyl hexyl) sebacate, cotton seed oil, whale oil, castor oil, fluorocarbon oil, polyethylene oxide oil, silicone oil or glycerine.  Up to 70 per cent, e.g. 8-25 per cent, of siliceous material may be employed. Soaps and cleansing compositions.-The surface-esterified siliceous material may be used in conjunction with soap in cake or powder form, or with synthetic detergents, e.g. polyethylene oxide and Lorol trimethyl-ammonium chloride ("Lorol" is a Registered Trade Mark), or with silver and chromium metal polishes, rust removes, pickling liquids and metal cleaners of the oil-in-water emulsion, organic solvent and paste types.  Cleaner abrasives specified are diatomaceous earth, volcanic ash, aluminium oxide, carborundum, titanium dioxide and iron oxide.  Paints, lacquers and varnishes may comprise the surface-esterified siliceous material.  Polishing compositions may comprise the surface - esterified siliceous material and carnauba, candelilla, beeswax, montan, ozokerite, ceresin, paraffin wax, condensation product of hardened castor oil or octadecanediol with boric acid, monobasic carboxylic acid ester of perhydrogenated novolac, polyethylene adipate, or a polymerization product of ethylene and dichloroacetic or bromacetic acid.  A paste wax may contain 20-40 per cent of wax and up to 18 per cent of siliceous material.  An aqueous wax dispersion may contain 10-15 per cent of wax and 3-9 per cent of siliceous material and as dispersing agent mono-, di- or triethanolamine oleate or stearate, 2-amino 2-methyl 1-propanol, a sodium or potassium soap, morpholine oleate or monoethylamine oleate.  Protective polishes may contain the siliceous material and organo-silicon oils and lacquers.ALSO:Surface-esterified siliceous material (see Group III) may be used as a dispersing agent in resin dispersions or as a reinforcing filler, particularly in transparent and translucent resins.  Other fillers specified are wood flour, diatomaceous earth, carbon black, clay and cellulose.  Resins specified for the production of sheets, rods, tubes, supported and unsupported films, moulded and cast articles and powder are cumarone and indene resins, acetylene polymers and halogen derivatives, ethylene polymers, polytetrafluorethylene, polymerized butadiene, 2 : 3-dimethyl butadiene and 2-chlorobutadiene, butadiene copolymerized with styrene, acrylonitrile, methylmethacrylates and methylvinyl ketone, isobutylene copolymerized with isoprene, polystyrene, olefin - sulphur dioxide resins, resins formed by oxidation or chlorination of petroleum constituents or reaction thereof with formaldehyde, methylal, metallic halides, sulphur or sulphur chloride, caseinformaldehyde, terpene-phenelic resins, condensation products of formaldehyde with phenol, urea, thiourea, melamine, dicyandiamide and resorcinol, phenol - resorcinol - formaldehyde resins, phenol-furfural resins, furane resins, ketone resins, co-condensation products of melamine-formaldehyde resins and diglycol carbamate, copolymers of diallyl phenyl phosphonate with methyl methacrylate, vinyl acetate, diallyl phthalate, diallyl succinate, diallyl oxalate and unsaturated alkyd resin mixtures, condensation products of phthalic anhydride, maleic anhydride or sebacic acid with glycerol, pentaerythritol or sorbitol, sulphonamide-aldehyde resi