Patent GB-779288-A (GB)
Title: Improvements in or relating to flameproofing compositions
IPC: C09D5/18
Filed: 1955-01-17
Abstract: A flameproofing composition comprises a chlorinated organic material containing at least 50 per cent by weight of chlorine and an antimony, arsenic or bismuth derivative of an organic material, the metal or metalloid being bound through an oxygen linkage to the organic component of the derivative.  The composition may be incorporated into synthetic rubber or synthetic resins, e.g. unsaturated polyester resins, polyvinyl chloride polystyrene, cellulose acetate butyrate or propionate, cellulose acetate, cellulose ether resins, ethyl cellulose, polymethyl, ethyl, isopropyl and butyl methacrylates, polyethylene and cellulosic and synthetic fibre fabrics.  The chlorinated organic material preferably comprises more than eight carbon atoms, e.g. derivatives of paraffin and other oils and waxes, fats, higher fatty acids, and higher fatty esters. The antimony, arsenic or bismuth derivative may be that of a carboxylic acid such as glycollic, lactic, salicylic, citric, malic, tartronic, mucic, tartaric, oxalic, fumaric, malonic and adipic acids, of gallic or oxybenzoic acid, of phenols such as catechol and pyrogallol, or of amino, amido and halogen acids.  The derivative may also be that of a polybasic carboxylic acid in which the hydrogen of one of the carboxyl groups is replaced by alkali or alkaline earth metals, alkyl, alkylene, aryl, aralkyl, aralkylene, alkaryl or a saturated hydrocarbon such as cyclohexene, or cyclohexane.  Ammonium and amine salts may also be used.  The preferred derivatives are potassium, ammonium, barium and ethylenediamine antimonyl tartrates, and antimonyl catechol.  The chlorinated organic material which dissociates when a flame is applied thereto is stabilized against premature decomposition at normal temperature by the addition thereto of derivatives of ethylene oxide such as propylene oxide, butylene oxide, phenyl ethylene oxide, tolyl ethylene oxide, diphenyl ethylene oxide, phenoxy propylene oxide, diethyl ethylene oxide, benzyl ethylene oxide, epichlorhydrin, glycide or its ethers, e.g. the methyl-, ethyl-, propyl, tolyl-, alpha or beta naphthyl ethers, cyclopentene oxide or cyclohexene oxide.  Other stabilizers specified are an alkaline earth metal salt of an aliphatic acid, e.g. strontium caprylate and tetra aryl or alkyl substituted compounds of tin, e.g. tetra butyl tin, tetra phenyl tin, dibutyl diphenyl tin, or dibutyl tin dilaurate.  A plasticiser, e.g. tricresyl, triphenyl and ethyl hexyl phosphates, dibutyl and dioctyl phthalates, dioctyl sebacate, butyl ricinoleate, triethylene glycol di-2-butyrate, amyl laurate, and toluene ethyl sulphonamides, may be added to the flameproofed composition either before or during the compounding of the composition with the material to be flameproofed.  Lubricants such as oleic and stearic acids and their alkaline earth salts may be present.  As a stabilizing agent against decomposition by ultra-violet light, the flameproofed composition may have incorporated therein phenyl, methyl, ethyl or menthyl salicylate, alpha, beta, methyl or methyl aceto umbelliferone, menthyl anthranilate, substituted benzophenone, e.g. bis-(2 - hydroxy, 5 - chloro) benzophenone, ethyl p-amino benzoate, quinine disulphate, quinine oleate, and oxyquinoline sulphate.  The flame-proofing composition may be added to the unpolymerized, partially polymerized or fully polymerized materials.  In examples a translucent glass fibre reinforced panel is made by mixing a polyester resin, styrene, chlorinated paraffin wax, potassium antimonyl tartrate and a polymerization catalyst including benzoyl peroxide and tricresyl phosphate, pouring the mixture upon a glass fibre mat in a panel mould, and curing at about 270 DEG  F.  Many applications are specified.  Specification 652,669 and U.S.A. Specifications 2,333,639 and 2,445,553 are referred to.ALSO:A flameproofing composition comprises a chlorinated organic material containing at least 50 per cent by weight of chlorine and an antimony, arsenic, or bismuth derivative of an organic material, the metal or metalloid being bound through an oxygen linkage to the organic component of the derivative. The composition may be incorporated into natural rubber, or synthetic resins, e.g., polyester resins, polyvinyl chloride and other polyvinyl resins, glycol-saturated dicarboxylic poly-unsaturated dicarboxylic acid resins, polystyrene, cellulose acetate butyrate or propionate, cellulose acetate cellulose ether resins, ethyl cellulose, methyl methacrylate or derivatives, polyethylene, paper, wood, cellulosic and synthetic fibre fabrics, and paints. The chlorinated organic material preferably comprises more than eight carbon atoms, e.g. paraffin and other oils and waxes, fats, higher fatty acids, and higher fatty esters.  The antimony, arsenic, or bismuth derivative may be that of a carboxylic acid such as glycollic, lactic, salicylic, citric, malic, tartronic, mucic, tartaric, oxalic, fumaric, malonic, and adipic acids, or of gallic, or oxybenzoic acid, phenols such as catechol and pyrogallol, amino, amido, and halogen acids.  The derivative may also be that of a polybasic carboxylic acid in which the hydrogen of one of the carboxyl groups is replaced by alkali or alkaline earth metals, alkyl, alkylene, aryl, aralkyl, aralkylene, alkaryl, or a saturated hydrocarbon such as cyclohexene or cyclohexane. Ammonium and amine salts may also be used.  The preferred derivatives are potassium, ammonium, barium, and ethylene-diamine antimonyl tartrates, and antimonyl catechol.  The chlorinated organic material which dissociates when a flame is applied thereto is stabilized against premature decomposition at normal temperature by the addition thereto of derivatives of ethylene oxide, propylene oxide, butylene oxide, phenyl ethylene oxide, tolyl ethylene oxide, diphenyl ethylene oxide, phenoxy propylene oxide, diethyl ethylene oxide, benzyl ethylene oxide, epichlorhydrin, glycide or its ethers, e.g. methyl-, ethyl-, propyl, tolyl-, alpha or beta naphthyl or cyclopentene oxide, or cyclohexene oxide, an alkaline earth metal salt of an aliphatic acid, e.g. strontium caprylate, tetra aryl or alkyl substituted compounds of tin, e.g. tetra butyl tin, tetra phenyl tin, dibutyl diphenyl tin, or dibutyl tin dilaurate.  A plasticizer, e.g. tricresyl phosphate, may be added to the flameproofed composition either before or during the compounding of the composition with the material to be flameproofed.  As a stabilizing agent against decomposition by ultra violet light the flame-proofed composition may have incorporated therein phenyl, methyl, ethyl, or menthyl salicylate, alpha, beta, methyl or methyl aceto umbelliferone, menthyl anthranilate, substituted benzophenone, og. bis (2 hydroxy, 5 chloro) benzophenone, ethyl p-amino benzoate, quinine disulphate, quinine oleate, and oxyquinoline sulphate.  In one of the described examples a translucent glass fibre reinforced panel is made by mixing a polyester resin, chlorinated paraffin wax, potassium antimonyl tartrate, and a polymerization catalyst including benzoyl peroxide and tricresyl phosphate, pouring the mixture upon a glass fibre mat in a panel mould, and curing at about 240 DEG F.  Specification 652,669 and U.S.A. Specifications 2,333,639, 2,445,553 and Application 397,741 are referred to.