Patent GB-489311-A (GB)
Title: Improvements in or relating to the manufacture of substituted carboxylic acid amidesand their polymerisation products
IPC: C08F20/52
Filed: 1937-01-25
Abstract: Acyl substituted carboxylic acid amides are manufactured by reacting together an ester of an a -methylene monocarboxylic acid and an alkali metal amide, i.e. a carboxylic acid amide in which one or more amido hydrogen atoms are replaced by an alkali metal. The reaction may be effected by condensing the ester with the alkali metal amide in the presence of a catalyst comprising a lower saturated alcohol or a ketone, e.g. isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, amyl alcohol, acetone, methyl propyl ketone, dibutyl ketone, ethyl propyl ketone and their homologues.  The catalyst may act as a solvent, or other substances, e.g. benzene or toluene, may be employed as solvents. Alternatively the alkali metal amide may be formed in situ in liquid ammonia in the presence of the ester, the use of catalysts being usually dispensed with in this case.  To produce monoacylated amides there are preferably employed equivalent proportions of the ester and the monoalkali metal amide.  To produce polyacylated amides, two or more molecular proportions of the ester may be reacted with one of a polyalkali metal amide, but preferably the monoacylated amide is first produced from equimolecular proportions of the ester and a monoalkali metal derivative of an amide having a plurality of hydrogen atoms (attached to the same or different nitrogen atoms) replaceable by metal, converted into its alkali metal derivative, e.g. by the action of sodium in liquid ammonia, and the product reacted with a further molecular proportion of the ester.  In examples: (1) sodium is added to a solution of methyl methacrylate and formamide in liquid ammonia to produce monomethacrylylformamide; (2) methyl methacrylate and sodium urea (prepared by the interaction of equivalent quantities of sodium and urea in liquid ammonia) are reacted in the presence of acetone, yielding methacrylylurea; alternatively the reaction is effected as in (1); (4) methyl methacrylate and sodium phenyl urea (prepared by the interaction of equivalent quantities of sodium and phenylurea in liquid ammonia) are reacted in the presence of acetone, producing methacrylylphenylurea; the sodium phenylurea may be used without isolation from its solution in liquid ammonia.  Polymerization products are manufactured by polymerizing the products described above, preferably in the presence of oxygen-containing catalysts, e.g. organic peroxides, peracids or per-salts, if desired in the presence of other polymerizable bodies, e.g. acrylic and methacrylic acids or vinyl compounds such as vinyl acetate or methyl vinyl ketone, and of modifying agents, e.g. plasticizers, fillers or pigments.  Polymerization may be effected by the action of heat of ultra-violet light of both, if desired in aqueous or other liquid media.  The products are useful in the coating, sizing, impregnating and moulding arts. Those which are soluble in dilute caustic solutions can be regenerated therefrom by acids, and may be used for preparing films by brushing, spraying or flowing the alkaline solutions on to glass or metal and immersing in dilute solutions (e.g. 5 per cent) of hydrochloric, sulphuric, acetic or other acids. In examples: (3) methacrylyl urea is heated in alcohol with benzoyl peroxide; (5) methacrylylphenylurea is similarly polymerized; (6) a 1 : 9 mixture of methacrylylurea and methyl methacrylate is heated with benzoyl peroxide in aqueous methanol; the product is moulded; interpolymers of the constituents in other proportions ranging to 9 : 1 are described, those containing 80 per cent of methacrylylurea being soluble in aqueous alkali; (7) mixtures of methacrylylurea and cyclohexyl methacrylate are heated in dioxane with benzoyl peroxide; the products are compatible with drying oils; (8) a mixture of methacrylylurea and n propyl or isobutyl methacrylate is similarly polymerized; the products are compatible with drying oils and oil-modified polyhydric alcohol - polybasic acid resins; (9) a mixture of methacrylylurea and methyl acrylate is similarly polymerized; (10) an aqueous emulsion of methacrylylurea and vinyl acetate is heated with benzoyl peroxide; (11) mixtures of methacrylylurea and methyl vinyl ketone, if necessary with the addition of solvents, e.g. ethanol or dioxane, are exposed to ultraviolet light; (12) a mixture of methacrylylphenylurea and methyl methacrylate is heated in alcohol with benzoyl peroxide.