Patent GB-805380-A (GB)
Title: N-acryloxyacetamidoalkyl-n,n-alkyleneureas
IPC: C08F20/34
Filed: 1956-08-07
Abstract: Polymers and copolymers of compounds of the formula <FORM:0805380/III/1> are used as flocculants to clarify aqueous suspensions, such as those of clay or minerals, and also to make coatings on substrates such as textiles, leather, paper, wood, metal or glass; for this purpose they can be mixed with other film-forming agents (such as vinyl or acrylic resins) and may be pigmented or dyed.  Emulsion copolymers provide water-base paints.  In examples: (1) a solution is made by heating b  - (a  - methacryloxyacetamides) - ethylethyleneurea, methyl methacrylate, ethoxyethyl acetate and azo-di-isobutyronitrile and coated on wood, glass or metal panels; (2) copolymers of the above compounds with methyl methacrylate with or without butyl methacrylate or acrylonitrile are cast on glass panels and baked; the hardness is increased by the addition of oxalic acid and bis-(methoxymethyl)-urea; the coatings can be pigmented or plasticized with dibutyl phthalate and applied to metal surfaces directly or over primers.ALSO:The invention comprises polymers and copolymers of acrylic derivatives of the formula <FORM:0805380/IV (a)/1> where R is H or methyl and A is C2 or C3 alkylene. Polymerization may be effected in bulk, solution, emulsion or suspension, using as catalyst an inorganic or organic peroxide, a persulphate or an azo compound; suitable catalysts of these types are mentioned.  There may also be present a reducing agent (e.g. a sulphite or hydrazine) and/or a mercaptan such as mercaptoethanol as regulator.  Emulsifiers that are suitable include anionic, cationic and non-ionic types.  Specified constituents of the copolymers are vinyl ethers (alkyl, hydroxyalkyl and ureidoalkyl), vinyl esters, vinyl thioethers, allyl esters, styrene and its derivatives (e.g. methyl- and chloro-), vinylnaphthalene, vinylpyridine, vinylcarbazole, acrylic and methacrylic acids, salts, nitriles, esters (alkyl and dialkylaminoalkyl), amides (which may be N-alkyl or N-dialkylaminoalkyl), maleic, fumaric and itaconic acids and esters, maleic anhydride, diethyl citraconate and diethyl chloromaleate. There may be two or more polymerizable groups present, as in diand tri-vinylbenzenes, ethylene diacrylate and methacrylate, bis - (vinyloxyethyl) - urea and vinyloxyethyl acrylate and methylrylate. Mixed copolymers can be made with methyl methacrylate and methyl or butyl acrylate.  The polymers can be added to coating, adhesive and film-forming compositions, and may be pigmented or dyed for this purpose.  The homopolymers or their reaction products with formaldehyde can be combined with ureaformaldehyde or triazine-formaldehyde resins.  Copolymers with acrylonitrile can be made into fibres or films.  Copolymers with acrylic or methacrylic acid or with vinylpyridine can be added to melts or solutions of acrylonitrile copolymers to modify the dyeing properties of fibres and films made therefrom. Examples show the polymerization of b -(a -methacryloxyacetamido) - ethyl - ethyleneurea, g  - (a  - methacryloxyacetamido) - propyl - trimethyleneurea and b -(a -acryloxyacetamido)-ethyl-ethyleneurea, and the reaction of the first two with formaldehyde.  Specific copolymers are made from acrylic acid, methyl acrylate, 4-vinylpyridine (product reacted with formaldehyde), N - methyl - N - vinyloxyethyl - melamine, methyl methacrylate, methyl+butyl methacrylate, lauryl+myristyl methacrylate and methyl methacrylate+acrylonitrile.  In a further example various copolymers (with or without oxalic acid and bis-(methoxymethyl)-urea) are cast into films on glass and baked; these coatings may be pigmented or plasticized with dibutyl phthalate.  In a final example a mixture of a monomer, methacrylic acid, methyl methacrylate, formaldehyde in methanol and acetyl peroxide in dimethyl phthalate is cast between glass plates.  The monomers of the above formula are useful as plasticizers and may be incorporated in fibres, films, sheets or rods of polyamides or various vinyl polymers and copolymers, preferably by addition to the melt, solution or dispersion before the final extrusion or moulding.  In an example a mixture of b -(a -methacryloxyacetamido) - ethyl - ethyleneurea and a vinyl chloride-acetate copolymer in acetone is cast into a film.  The monomers may also be applied with glycerol or glycols as softeners to pellicles, films or sheets of regenerated cellulose or hydroxyethyl-cellulose.  A further use of the monomers (or their formaldehyde reaction products) is as modifiers in aminoplast resins to increase the toughness and water-resistance; they may react with the formaldehyde or lower alkanol present in the aminoplast composition.  Urea-formaldehyde and melamine-formaldehyde condensates may be treated in this way.ALSO:The invention comprises compounds of the formula <FORM:0805380/IV (b)/1> where R is H or methyl and A is alkylene of 2 or 3 carbon atoms. These are made by reacting alkali metal or silver acrylates and methacrylates with cyclic ureas of the formula <FORM:0805380/IV (b)/2> where X is chlorine or bromine, preferably in the presence of a catalyst (tertiary amine or quaternary compound) and a polymerization inhibitor; acetonitrile is the preferred solvent. The products react at the double bond with alcohols, mercaptans, primary and secondary amines, nitroalkanes, malonates, acetoacetates and sodium bisulphite, in particular with dodecylamine and mercaptan.  Examples show the preparation of 1-(b -methacryloxyacetamidoethyl) - imidazolidine - 2 - one, 1 - (b  - acryloxyacetamido - ethyl) - imidazolidine - 2 - one, 1-(g  - methacryloxyacetamido - propyl) - hexahydropyrimidine - 2 - one and 1 - (g  - acryloxyacetamidopropyl) - hexahydropyrimidine - 2 - one. The products may also be reacted with formaldehyde.  Halo-acetamido compounds of the second formula above are made by reacting alkyl halo-acetates with compounds of the formula <FORM:0805380/IV (b)/3> in a solvent such as methanol, with external cooling.  Examples are given of the preparation of 1 - (b  - chloracetamido - ethyl) - imidazolidine - 2 - one and 1 - (g  - chloracetamido - propyl) - hexahydropyrimidine - 2 - one.  1 - (b  - aminopropyl) - 5 - methyl - imidazolidine-2-one may also be used as starting material.ALSO:Compounds of the formula <FORM:0805380/IV (c)/1> in which R is H or methyl and A is C2 or C3 alkylene, react with long-chain (e.g. dodecyl) amines and mercaptans to give agents useful for softening and lubricating textiles such as cotton and rayon. Polymers and copolymers of the above are used in solution or with starch, gelatine or plasticizers therefor as warp sizes. Copolymers with ethyl or butyl acrylate are applied to wool from aqueous dispersion (e.g. by padding) and the treated fabric heated to 240-350 DEG  F.; it then shows reduced shrinkage on laundering. An example of this latter process is given.ALSO:Polymers and copolymers of compounds of the formula <FORM:0805380/II/1> especially those of molecular weight 20,000 to 50,000, are useful as flocculants in the clarification of aqueous systems containing clays or other finely-divided materials, especially mineral matter produced in the grinding of ores.