Patent GB-595758-A (GB)
Title: Production of resins
IPC: C08F18/20
Filed: 1944-10-23
Abstract: Esters of unsaturated alcohols having an olefinic double bond and nuclearly halogenated aromatic carboxylic acids in which at least half of the nuclear hydrogen atoms not substituted by carboxy radicals are replaced by halogen, are polymerized alone or with an organic compound having an unsaturated carbon to carbon group by the effect of heat with or without light.  Esters specified are diallyl tetrachlorophthate, dimethallyl tetrachlorophthalate, dichlorallyl-, dicrotyl-, divinyl-, di-isopropenyl-, allyl vinyl, allyl methallyl-, allyl crotyl-, allyl isopropenyl-, methallyl vinyl-, crotyl vinyl tetrachlorophthalates and the corresponding bromine and fluorine containing esters, diallyl, dimethallyl, divinyl, allyl vinyl, methallyl vinyl dichlorophthalates, allyl and methallyl pentachlorobenzoates, allyl tetrachlortoluate, allyl trichlorodimethylbenzoates and allyl dichlorodimethylphthalates. Specified monomers which may be used in conjunction are styrene, alphamethyl styrene, vinyl naphthalenes, vinyl and vinylidene halides, vinyl acetate, propionate, butyrate, valerate and benzoate, vinyl ethers, methyl acrylate, methyl methacrylate, allyl halides, allyl acetate and propionate, vinyl, allyl and methallyl esters of oxalic, phthalic, malonic, glutaric, adipic, sebacic, citric, tricarballylic, isophthalic and naphthalic dicarboxylic acids, vinyl, allyl and methallyl ethers of glycol, diethylene glycol, triethylene glycol, trimethylene glycol, propylene glycol, glycerol, diglycerol, pentaglycerol and pentaerythritol, acrylates, methacrylates and crotonates of these alcohols and vinyl, allyl or methallyl esters of acrylic, methacrylic, chloracrylic, crotonic, itaconic, citraconic and cinnamic acids, of phosphoric acids and of ortho acids of silicon and boron, vinyl acetylene, divinyl acetylene, 1 : 3-butadiene, 2-chloro-1 : 3-butadiene, isoprene and conjugated penta-, hexa-, hepta-, octa-, nona- and deca-dienes.  The polymerization may be carried out in bulk, solvent or dispersion and in the presence of acetyl, benzoyl acetyl, lauryl, di-butyryl, succinyl, sodium, barium, tertiary butyl hydro-peroxides, peracetic and perphthalic acids, perborates, persulphates, ozone and oxygen, or di-(tertiary butyl) peroxide, mixed if desired with inhibitors such as tannic acid, hydroquinone, thiophene, benzoquinone, thiobenzaldehyde, anhydroformaldehyde, arylamines and triphenyl amines.  Partial polymers may be mixed, or monomers may be added to a partial polymer or copolymer and the polymerization completed.  Esters having two or more unsaturated groups may be partially polymerized to a fusible stage, shaped in moulds or by extrusion and polymerized to the infusible state, more catalyst being added if desired.  The products may be mixed with natural resins, cellulose derivatives, drying oils, solvents such as toluene, alkyd, urea-aldehyde, phenol-aldehyde resins, polyamides and polyester amides, plasticisers, lubricants, dyes, pigments and fillers, and where such substances are inert they may be added to the monomers. Films and coatings made from the polymers are fire resistant. Fabric and paper can be impregnated with emulsions, solutions or undiluted fusible polymers, and the polymerization completed. The esters of halogenated aromatic carboxylic acids with unsaturated alcohols are prepared by direct esterification; reacting a metallic salt of the acid with a halide of the alcohol; reacting a halide of the acid with a metallic alcoholate; reacting a halogenated acid with an ester of an unsaturated alcohol with a lower saturated carboxylic acid; or reacting an unsaturated alcohol with an ester of a halogenated acid with a saturated alcohol.  Specification 549,234 is referred to.