Patent GB-490007-A (GB)
Title: Propyl methacrylate its manufacture and applications
IPC: C07C69/54
Filed: 1937-02-03
Abstract: n-Propyl methacrylate is manufactured by reacting n-propyl alcohol with a lower ester of methacrylic acid, preferably in the presence of an ester-interchange catalyst, or with a methacrylyl halide.  In an example, n-propyl alcohol is heated with methyl methacrylate in the presence of concentrated sulphuric acid and hydroquinone. Polymerization products are manufactured by polymerizing monomeric n-propyl methacrylate by means of heat, light and/or a polymerization catalyst, e.g. oxygen, ozone, an organic peroxide, an ozonide, aluminium sulphate, boron fluoride, a mineral acid, e.g. hydrochloric or sulphuric acid, an organic acid, e.g. acetic or methacrylic acid, or the anhydride or halide thereof, or metal salts of fatty or resinic acids, e.g. cobalt or manganese oleate or resinate, in the presence or absence of a solvent for both monomer and polymer, or in the presence of a solvent for the monomer and non-solvent for the polymer, or in emulsion.  The n-propyl methacrylate may be interpolymerized with other polymerizable compounds such as polymerizable compounds of methacrylic or acrylic acids, particularly methyl methacrylate, or vinyl compounds, or separately produced polymers may be subsequently mixed.  There may be incorporated before, after, or in some cases during polymerization, plasticizers or other p  modifying agents, e.g. camphor; phthalates, e.g. ethyl, propyl, isopropyl, butyl, isobutyl, cyclohexyl, methylcyclohexyl or benzyl phthalates, or mixed phthalates, e.g. cyclohexyl-butyl, benzyl-butyl or butyl-lauryl phthalates; esters of other dibasic acids, e.g. the ethyl, propyl, isopropyl, butyl, isobutyl, cyclohexyl, methylcyclohexyl or benzyl esters of succinic, fumaric, tartaric, adipic and sebacic acids; esters of monobasic acids, e.g. the butyl, isobutyl, cyclohexyl, methylcyclohexyl, benzyl or lauryl esters of lauric, laevulinic, benzoic, benzoylpropionic and benzoylbenzoic acids; esters of polyhydric alcohols such as glycol and glycerol, e.g. glycol benzoate, glycol laevulinate, triacetin, tripropionin and tributyrin; the ether alcohol esters of polycarboxylic acids, e.g. methoxyethyl and ethoxyethyl phthalates; substituted toluenesulphonamides, e.g. ethyl p-toluenesulphonamide; substituted amides, e.g. tetraethylphthalamide, hydrocarbons, e.g. dixylylethane; halogenated hydrocarbons, e.g. chlorinated diphenyls and dichlordibenzyl; ether compounds such as dicresoxyethyl ether; tricresyl phosphate; drying, semi-drying or non-drying oils, e.g. castor oil, cotton seed oil or linseed oil; synthetic and natural resins, waxes, bitumens; cellulose derivatives, e.g. cellulose nitrate or ethyl cellulose; dyes, pigments or fillers, e.g. zinc oxide.  Polymerization may be carried out in an incomplete manner to yield a syrupy product; this can be used directly or with solvents or diluents for the production of coating, painting or impregnating compositions, e.g. for use on porous substances such as wood, paper, textile fabric or artificial stone, polymerization being subsequently completed, or it may be mixed with comminuted matter, e.g. ground cork or ground wood, fibrous substances or mineral fillers, the mixture being shaped and polymerization completed.  Shaped articles, e.g. umbrella handles, fountain pen barrels or buttons, may be produced by carrying out the polymerization in a mould, or the polymerization products may be shaped after softening with volatile solvents, which are subsequently evaporated, or they may be softened and kneaded, rolled, compressed, drawn into wires or threads, rolled into plates of films, pressed into shapes such as buttons or combs, or worked by cutting, sawing or filing.  The shaped articles may be polished, and parts connected together by smearing the faces with a solvent, e.g. acetone, butyl acetate or propyl methacrylate. The polymerization product dissolved in a solvent, which may be the monomer, may be transformed into films or fibres by casting or by extrusion into a precipitating bath or drying atmosphere. Coating-compositions, e.g. for table tops, refrigerators or the inner surfaces of food and beverage containers, may be obtained from mixtures of propyl methacrylate polymer with alkyd resins, especially oil modified alkyl resins, e.g. soya bean oil modified alkyl resin, with or without pigments, whilst nitrocellulose lacquers are obtainable from propyl methacrylate polymer, nitrocellulose, pigments, plasticizers and solvents, and clear varnishes from propyl methacrylate polymer, chinawood oil and oil-soluble phenol-aldehyde resin.  Solid, semi-solid or plastic polymerization products may be softened by heating, by addition of solvents, or both, and used in the softened state, e.g. as substitutes for horn, amber, artificial resins, lacquers, for impregnation purposes and for the production of films, pressure adhesives, artificial threads or interlayers for safety glass. For the production of safety glass the polymers or interpolymers may be used alone or with plasticizers, in the unpolymerized, partially polymerized or completely polymerized condition, polymerization being completed where necessary by subjecting the composite to light or heat or both.  Examples describe the polymerization of n-propyl methacrylate by heating with benzoyl peroxide in the presence of (1) aqueous methanol; (2) toluene. Specification 15271/14, [Class 2 (iii)], is referred to. Specification 467,900 also is referred to in the Provisional Specification.