Patent GB-351508-A (GB)
Title: Improvements in the manufacture and production of artificial masses and articles therefrom
IPC: C08F8/00
Filed: 1930-02-24
Abstract: Polymerized unsaturated aliphatic acids such as acrylic acid and their derivatives are produced by polymerizing the acid halides or nitriles, and reacting the products with substances having a reactive hydrogen atom such as water, inorganic bases, mono- and polyhydric alcohols, hydrogen sulphide, mercaptans, ammonia, primary and secondary amines, amides, and organic compounds containing a reactive methylene or methine group such as malonic or acetoacetic esters. The acid halides or nitriles may be polymerized in any known or suitable manner, and before polymerization may be mixed with one another or with other polymerizable compounds such as vinyl acetate, acrylic esters, or styrene.  The treatment of the polymerized halide or nitrile with the substance having a reactive hydrogen atom may be effected in presence of an inert diluent such as esters of carboxylic acids or dioxane in the case of the halide and concentrated sulphuric or phosphoric acid in the case of the nitrile.  Both halides and nitriles yield the corresponding acids or salts thereof when treated with water or alkali solutions, but the nitriles in presence of less than the equivalent quantity of water yield amides.  The halides yield esters with primary, secondary, and tertiary aliphatic, cycloaliphatic, and aromatic saturated and unsaturated alcohols; amides or diketopiperidine compounds with ammonia; amides or diketopiperidine compounds with primary and secondary aliphatic, cycloaliphatic, and aromatic saturated or unsaturated mono- or poly-amines such as methyl and butylamines, ethylene diamine, aniline, and cyclohexylamine and with amides such as formamide and acetamide; thio derivatives with hydrogen sulphide or mercaptans; and ketones with ethyl malonate or acetoacetate or the like or with hydrocarbons in the presence of aluminium chloride.  Instead of using one reagent to react with the polymerized halides or nitriles, several different reagents may be brought into reaction therewith, simultaneously or successively, and inert substances such as fillers may be added at any stage.  The products may be used in the preparation of coating-compositions or artificial masses which may contain cellulose esters or ethers; as plastifiers in the production of threads, films, and coating-compositions containing cellulose esters or ethers.  Pliable and elastic films resembling leather may be made from mixtures of 4 parts nitrocellulose with 1 part polymeric esters; and hard films with high resistance to breakage by bending from mixtures of 1 part of nitrocellulose with 1 part of the polymeric esters.  Mixtures of the polymeric esters and amides yield films or threads resembling those prepared from cellulose esters, and the products which have been produced in presence of vinyl compounds are particularly suitable for the production of solid articles obtained by moulding.  The products may be vulcanized with the aid of sulphur.  In the examples, polymerized acrylic acid chloride dissolved in butyl acetate is condensed with ethyl alcohol, allyl alcohol, aniline, formamide, isobutylamine, glycerin, and ethyl mercaptan respectively; polymerized acrylic acid chloride is reacted with moist air, water at 120 DEG  C., and butyl alcohol respectively; ammonia is led into a solution of polymerized acrylic acid chloride in dioxane; polymerized acrylic acid nitrile is heated with caustic soda solution under reflux, and with concentrated ammonia at 130 DEG C. in an autoclave; polymerized acrylic acid nitrile made in presence of styrene is emulsified in aqueous solution of sodium dibutylnaphthalene sulphonate (prepared as described in Specification 346,817, [Group XII], and sodium oleate, and heated with caustic soda to 130-140 DEG  C. in an autoclave.ALSO:Polymerized unsaturated aliphatic acids and their derivatives; printing.-Polymerized unsaturated aliphatic acids such as acrylic acids and their derivatives are produced by polymerizing the acid halides or nitriles, and reacting the products with substances having a reactive hydrogen atom such as water, inorganic bases, mono- and polyhydric alcohols, hydrogen sulphide, mercaptans, ammonia, primary and secondary amines, amides, and organic compounds containing a reactive methylene or methine group such as malonic or acetoacetic esters. The acid halides or nitriles may be polymerized in any known or suitable manner, for instance in the case of the halides by means of natural or artificial light with or without catalysts such as high molecular amines such as triethylene tetranine, NH2-C2H4-NH-C2H4-NH-C2H4 NH2 (obtained by reacting 3 mols. of ethylidene chloride with 4 mols. of ammonia) or dipiperidyl, or, in the case of the nitriles, by emulsifying them and heating to 100 DEG C. with or without catalysts such as hydrogen peroxide or benzoyl peroxide, and the halide or nitrile before polymerization may be mixed with one another or with other polymerizable compounds such as vinyl acetate, acrylic esters, or styreno.  The treatment of the polymerized halide or nitrile with the substance having a reactive hydrogen atom may be effected in presence of an inert diluent such as esters of carboxylic acids or dioxane in the case of the halide, and concentrated sulphuric or phosphoric acid in the case of the nitrile. Both halides and nitriles yield the corresponding acids or salts thereof when treated with water or alkali solutions, but the nitriles in presence of less than the equivalent quantity of water yield amides.  The halides yield esters with primary, secondary, and tertiary aliphatic, cycloaliphatic, and aromatic saturated and unsaturated alcohols; amides or diketopiperidine compounds with ammonia; amides or diketopiperidine compounds with primary and secondary aliphatic, cycloaliphatic, and aromatic saturated or unsaturated mono- or polyamines such as methyl and butylamines, ethylene diamine, aniline, and cyclohexylamine and with amides such as formamide and acetamide; thio derivative with hydrogen sulphide or mercaptans; and ketones with ethyl malonate or acetoacetate or the like or with hydrocarbons in the presence of aluminium chloride. Instead of using one reagent to react with the polymerized halides or nitriles, several different reagents may be brought into reaction therewith, simultaneously or successively, and inert substances such as fillers may be added at any stage.  The products may be used in the preparation of coating-compositions or artificial masses which may contain cellulose esters or ethers; as plastifiers in the production of threads, films, and coating compositions containing cellulose esters or ethers; and the acids or their salts may be used as thickening agents in the preparation of printing-pastes.  Pliable and elastic films resembling leather may be made from mixtures of 4 parts nitrocellulose with 1 part polymeric esters; and hard films with high resistance to breakage by bending from mixtures of 1 part of nitrocellulose with 1 part of the polymeric esters.  Mixtures of the polymeric esters and amides yield films or threads resembling those prepared from cellulose esters, and the products which have been produced in presence of vinyl compounds are particularly suitable for the production of solid articles obtained by moulding. The products may be vulcanized with the aid of sulphur.  In the examples, polymerized acrylic acid chloride dissolved in butyl acetate is condensed with ethyl alcohol, allyl alcohol, aniline, formamide, isobutylamine, glycerin, and ethyl mercaptan respectively; polymerized acrylic acid chloride is reacted with moist air, water at 120 DEG  C. and butyl alcohol respectively; ammonia is led into a solution of polymerized acrylic acid chloride in dioxane; polymerized acrylic acid nitrile is heated with caustic soda solution under reflux and with concentrated ammonia at 130 DEG  C. in an autoclave; polymerized acrylic acid nitrile made in presence of styrene is emulsified in aqueous solution of sodium dibutylnaphthalene sulphonate (prepared as described in Specification 346,817, [Group XII]), and sodium oleate and heated with caustic soda to 130-140 DEG C. in an autoclave, the viscous product being suitable for the production of printing-pastes.ALSO:Polymerized unsaturated aliphatic acids such as acrylic acid and their derivatives are produced by polymerizing the acid halides or nitriles, and reacting the products with substances having a reactive hydrogen atom such as water, inorganic bases, mono- and polyhydric alcohols, hydrogen sulphide, mercaptans, ammonia, primary and secondary amines, amides, and organic compounds containing a reactive methylene or methine group such as malonic or acetoacetic esters.  The acid halides or nitriles may be polymerized in any known or suitable manner, and before polymerization may be mixed with one another or with other polymerizable compounds such as vinyl acetate, acrylic esters, or styreno.  The treatment of the polymerized halide or nitrile with the substance having a reactive hydrogen atom may be effected in presence of an inert diluent such as esters of carboxylic acids or dioxane in the case of the halide and concentrated sulphuric or phosphoric acid in the case of the nitrile.  Both halide and nitriles yield the corresponding acids or salts thereof when treated with water or alkali solutions, but the nitriles in presence of less than the equivalent quantity of water yield amides.  The halides yield esters with primary, secondary, and tertiary aliphatic, cycloaliphatic, and aromatic saturated and unsaturated alcohols; amides or diketopiperidine compounds with ammonia; amides or diketopiperidine compounds with primary and secondary aliphatic, cycloaliphatic, and aromatic saturated or unsaturated mono- or polyamines, such as methyl and butylamines, ethylene diamine-, aniline, and cyclohexylamine and with amides such as formamide and acetamide; thio derivative