Patent GB-465789-A (GB)
Title: Esters of methacrylic acid, their manufacture and applications
IPC: C07C69/54
Filed: 1935-11-14
Abstract: Methacrylic acid esters are manufactured by reacting an unsaturated alcohol with methacrylic acid, methacrylic anhydride or methacrylyl chloride, or with the lower alkyl esters of methacrylic acid in the presence of an esterification catalyst. Suitable alcohols are mono- and polyhydric aliphatic and aromatic unsaturated alcohols, e.g. alkyl alcohol, crotyl alcohol, propargyl alcohol, alkyl substituted allyl alcohols, e.g. b -methylallyl alcohol, oleyl alcohols, alcohols made by hydrogenation of chinawood and castor oil acids and esters, and homologous alcohols.  In examples: (1) oleyl alcohol and methyl methacrylate are heated in the presence of benzene, hydroquinone p and p-toluene sulphonic acid, producing oleyl methacrylate; (2) the alcohols obtained by hydrogenating chinawood oils are similarly reacted; (3) b -methylallyl alcohol and methyl methacrylate are heated in the presence of benzene and phenylenediamine with gradual addition of sodium methylate, to yield b -methylallyl methacrylate. Polymerization products are manufactured by polymerizing the methacrylic acid esters described above by the action of heat, light and/or a polymerization catalyst, e.g. oxygen, ozone, an organic peroxide, an ozonide, aluminium sulphate, boron fluoride, mineral acids, e.g. hydrochloric or sulphuric acid organic acids, e.g. acetic or methacrylic acid, or their anhydrides or halides, metal salts of fatty acids an resinic acids, e.g. cobalt linoleate or resinate, manganese oleate or rosin, 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 methacrylic esters may be interpolymerized with other methacrylic, acrylic or vinyl esters, especially methyl methacrylate, or separately produced polymers may be subsequently mixed.  There may be incorporated before, after, or in some cases during polymerization, plasticizers or other modifying agents, e.g. camphor; tricresyl phosphate: 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 or glycerol, e.g. glycol benzoate or laevulinate, triacetin, tripropionin or tributyrin; substituted toluenesulphonamides, e.g. ethyl-p-toluenesulphonamide; substituted amides, e.g. tetraethylphthalamide, tetrabutylsuccinamide, tetrabutyladipamide; hydrocarbons, e.g. dixylylethane; halogenated hydrocarbons, e.g. chlorinated diphenyls or dichlordibenzyl; ether compounds, e.g. dicresoxyethyl ether; drying, non-drying or semi-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 ethylcellulose; dyes, pigments or fillers, e.g. zinc oxide.  Polymerization may be effected in an incomplete manner to yield a syrupy product which 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.  Solid, semi-solid or plastic polymerization products may be softened by heating, by addition of solvents, e.g. toluene, 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, the compositions being compounded with glass in the unpolymerized or partially or completely polymerized condition.  Rigid or flexible backings, e.g. metal, wood, stone, glass, shaped plastics, rigid articles made from or coated with cellulose derivative compositions, resins, cloth, paper, wire mesh, rubber, leather or regenerated cellulose films, may be coated or impregnated with the monomeric esters or solutions or emulsions thereof, and polymerization effected in situ.  In examples, (1) oleyl methacrylate is polymerized by heating with benzoyl peroxide at 100 DEG  C.; (2) methylallyl methacrylate is heated with benzoyl peroxide at 65 DEG  C. in aqueous methanol solution.  Specification 15271/14, [Class 2 (iii)], is referred to.