Patent GB-467900-A (GB)
Title: Esters of methacrylic acid and their manufacture
IPC: C08F20/10
Filed: 1935-12-20
Abstract: Esters of methacrylic acid with aliphatic monohydric saturated straight or branch chain primary alcohols containing more than five carbon atoms, aliphatic monohydric saturated secondary or tertiary alcohols containing more than five carbon atoms of the general formula <FORM:0467900/IV/1> or <FORM:0467900/IV/2> (where R1, R2 and R3 are similar or dissimilar alkyl groups, with or without substituted functional groups other than amino groups), aralkyl alcohols or alcohols derived from alkylated heterocyclic compounds are manufactured by reacting the said alcohols with a lower ester of methacrylic acid in the presence of an ester interchange catalyst or with a methacrylyl halide.  Suitable alcohols are: hexyl, heptyl, octyl, nonyl, decyl, dodecyl and higher homologous alcohols such as stearyl, cetyl and myristyl alcohol, the mixture of primary alcohols obtained by catalytic hydrogenation of carbon oxides at elevated temperatures and pressures, and the mixture of primary alcohols obtained by catalytic hydrogenation of coconut and like oils; ethyl propyl, ethylisopropyl, dipropyl, diisopropyl and propyl butyl carbinols which may be substituted by halogen or other substituent other than amino groups, higher secondary alcohols such as 3-methylpentanol-2, 2-methylpentanol-3, methyl diethyl, triethyl, propyl dimethyl and isopropyl dimethyl carbinol, and the keto-alcohols such as diacetone alcohol and the analogous keto-alcohols from similar or dissimilar lower ketones; furfuryl alcohol, b -phenylethyl alcohol, benzyl alcohol, the phenylalkyl carbinols such as phenyl methyl, phenyl ethyl, phenyl propyl and phenyl butyl carbinols, higher primary alkyl alcohols with one or more aryl groups substituted for hydrogen in the hydrocarbon chain, the o-tolylalkyl alcohols such as o-tolylmethyl, -ethyl and -propyl alcohols, triphenyl carbinol, naphthylalkyl and furfuryl alkyl alcohols.  In examples: (1) lauryl alcohol is heated with methyl methacrylate in the presence of concentrated sulphuric acid and hydroquinone, yielding lauryl methacrylate; (2) the mixture of alcohols obtained by hydrogenating coconut oil is similarly reacted; (3) the mixture of oxygenated organic compounds obtained by catalytic hydrogenation of carbon oxides is heated with methyl methacrylate, benzene, hydroquinone and p-toluenesulphonic acid; (4) stearyl alcohol is treated as in (3), but using sulphuric acid as catalyst, to produce stearyl methacrylate; (5) diisopropyl carbinol is heated with methacrylyl chloride to yield diisopropyl carbinol methacrylate; (6) b -phenylethanol is treated as in (4) to produce b -phenylethyl methacrylate; (7) furfuryl alcohol is heated with methyl methacrylate, benzene and phenylenediamine, with gradual addition of a solution of sodium methylate in methanol, yielding furfuryl methacrylate.  Polymerization products are manufactured by polymerizing the esters described above by the processes described in Specification 465,789, if desired with the addition of the modifyng agents ennumerated therein.  Interpolymers may be prepared with other polymerizable esters or other compounds of methacrylic or acrylic acids or vinyl compounds.  The polymers, mixed polymers and interpolymers may be used for the purposes set out in Specification 465,789.  They are also suitable for thermoplastic moulding, e.g. for the production of buttons or combs, or they may be softened and kneaded, rolled, compressed or drawn into wires or threads, or mixed with additional substances and rolled into plates or films, or dissolved in a solvent and cast or extruded to form a film.  Shaped articles, e.g. umbrella handles, fountain pen barrels or buttons, may also be obtained by effecting the polymerization in a suitable mould. The solid masses may be worked by cutting, sawing or filing, whilst the shaped articles may be polished, and parts connected together by smearing the faces with a solvent such as acetone, epichlorhydrin or the corresponding methacrylic ester.  The syrupy masses obtained by partial polymerization of the esters may be mixed with comminuted matter, e.g. ground cork, ground wood, fibrous substances or mineral fillers, the mixture then being shaped and polymerization completed. In examples: (8) lauryl methacrylate is heated in aqueous methanol with benzoyl peroxide; (9) the product of (2) above is similarly polymerized; (10) the product of (3) is similarly treated and the polymer is moulded into a disc or dissolved in toluene and the solution mixed with a butyl acetate solution of nitrocellulose and cast into a film; (11) stearyl methacrylate is heated with benzoyl peroxide; (12) diisopropyl methacrylate is polymerized as in (8) and the product is moulded into a disc; (13) b -phenylethyl methacrylate is similarly polymerized and moulded; (14) furfuryl methacrylate is similarly polymerized and moulded; (15) benzyl methacrylate (obtained by a process similar to that of (6) above) is similarly polymerized and moulded.  Specification 15271/14, [Class 2 (iii)], also is referred to.