Patent GB-835579-A (GB)
Title: Manufacture and use of new polymerisable condensation products
IPC: D06M15/39
Filed: 1956-12-24
Abstract: N - (b  - trichloro - a  - oxyethyl) - diamides of a  - b -unsaturated acyclic carboxylic acids are prepared by reaction between an a  : b -unsaturated cyclic mono- or di-carboxylic acid amide having at least one hydrogen atom bound to the amide nitrogen atom and chloral.  Suitable starting materials are the amides of furylacrylic acid, cinnamic acid, muconic acid, crotonic acid, acetylene dicarboxylic acid, phenyl-propiolic acid, methacrylic acid, or acrylic acid, or acrylic acid methylamide or methacrylic acid ethyl amide.  The reaction is preferably carried out with the use of equimolecular proportions of the reactants in the presence of an inert solvent such as benzene, toluene, hexane, chlorobenzene, chloroform, carbon tetrachloride, dioxane, tetrahydrofurane or dimethyl formamide, preferably at temperatures between 30-100 DEG  C. and preferably in the presence of a basic catalyst such as triethylamine, pyridine or dimethyl-aniline.  Examples are given of the preparation of N-(b -trichlor-a -oxyethyl) acrylic acid amide from acrylic acid amide, N - (b  - trichloro - a  - oxyethyl) - methacrylic acid amide from methacrylic acid amide, N - (b  - trichloro - a  - oxyethyl) - crotonic acid amide from crotonic acid amide and N - N - (b  - trichloro - a  - oxyethyl) - fumaric acid diamide from fumaric acid diamide.ALSO:The invention comprises homo and copolymers of N-(b -trichloro-a -oxyethyl) amides of a  : b -unsaturated acyclic carboxylic acids.  Compounds specified are N-(b -trichloro-a -oxyethyl)-acrylic acid amide, N-(b -trichloro-a -oxyethyl)-methacrylic acid amide, N-(b -trichloro-a -oxyethyl)-crotonic acid amide, and N : N1-(b  - trichloro - a  - oxyethyl) - fumaric acid diamide. The diamides are prepared by reacting the corresponding acid amide with chloral, and they may be polymerized with other unsaturated polymerizable compounds such as vinyl compounds, e.g. the acetate, formate, butyrate, benzoate, alkyl ketones or halides, vinyl aryl compounds such as styrene, ethyl, butyl or dodecyl acrylate, acrylonitrile, acrylic acid amide and derivatives thereof, and also analogous derivatives of methacrylic acid, a -chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, or acrylic or methacrylic acid itself.  Olefines such as isobutylene, butadiene, 2-chlorobutadiene or heterocyclic compounds containing at least one vinyl group may also be used. The polymerization process may take place in solution or in emulsion, preferably in the presence of one or more catalysts such as peracetic acid, acetyl peroxide, benzoylperoxide, benzoyl acetyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, para-methane hydroperoxide, hydrogen peroxide, percarbonates, persulphates or perborates.  The reaction may be enhanced by the use of heat and/or actinic rays and the speed of the polymerization or the molecular weight of the product may be regulated with e.g. mercaptans or terpenes.  The polymerization is preferably carried out at temperatures between 40 DEG -95 DEG  C, in the absence of air or oxygen and in the presence of an inert gas such as carbon dioxide or nitrogen, and in the presence of such activators as sulphur dioxide, sodium bisulphite, sodium sulphite, ammonium bisulphite, sodium hydrosulphite, sodium sulphate or water-soluble aliphatic tertiary amines such as triethanolamine or diethyl-ethanolamine.  A compound of a heavy metal, which is capable of existing in more than one state of valency and is present in the reduced state, or one or more complex cyanides of iron, cobalt, molybdenum, mercury, zinc, copper or silver may also be present.  When an emulsion is used as the reaction medium an anionic, cationic or non-ionic emulsifying agent should preferably be present such as the sulphuric acid esters of fatty alcohols, sulphonated castor oil, C12-C22 alkyl sulphonates, C12-C22 oxyalkyl sulphonates, especially sodium a -oxy-octadecane sulphonate, sulpho dicarboxylic acid esters, compounds of fatty amines with acetic, hydrochloric or sulphuric acids, salts of diethyl aminoethyl esters of fatty acids, salts of the type of oleylamidoethyl-diethylamine acetate, quaternary ammonium compounds such as cetyl - dimethyl - benzylammonium chloride, cetyl ester methosulphate, the quaternary compound of diethyl sulphate with triethanolamine tristearate, polyglycolethers of fatty acids, amines or alcohol such as octadecyl alcohol, the reaction products of 15-30 mols. of ethylene oxide with 1 mol. of the fatty alcohol, octyl-phenol polyglycol ethers, their acid sulphuric acid esters, glycerine monolaurate, or mixtures of such emulsifying agents with or without protective colloids such as alginates, tragacanth, agar-agar, polyvinyl alcohols, proteins, starches, or these colloids alone. When the polymerization is carried out in solution a solvent in which only the monomeric compounds are soluble, or a solvent in which both the monomer and polymer are soluble may be used.  The polymerization products may be used directly or may be modified by adding for example plasticizers such as dibutyl phthalate, or organic or inorganic pigments or fillers.  The polymers may be rendered insoluble by heating to e.g. 120-160 DEG  C., or they may be cross-linked with, e.g. di- or polyisocyanates, di- or polycarboxylic acids, epoxy resins, formaldehyde, hexamethylene tetramine, dimethylol-urea, p  methylol melamines and ethers thereof with alcohols of 1-6C, methylol compounds of acetylene- or ethylene-diurea or of uron, ethylene diamines, piperazine, diethylene triamine or other diamines and polyamines.  The cross-linking may take place in the presence of or absence of a carrier and solvent.  Heat or catalysts such as formic or acetic acid or ammonium chloride may also be used in the cross-linking reaction.  The polymers and co-polymers of the invention may be used as lacquer bases alone or with other lacquer resins such as ethers of ureaformaldehyde condensation products or melamine-formaldehyde condensation products, or added to rubber, leather, textiles, paper and pigments.  Examples are given of the preparation of poly-N-(b -trichloro-a -oxyethyl) acrylic acid amide and the corresponding methacrylic acid amide, also the preparation of co-polymers of the invention with isobutyl acrylate, n-butyl methacrylate, styrene, acrylonitrile, vinyl acetate, and of a process by rendering the polymers insoluble.  In Example (9) a copolymer of n-butylmethacrylate and N-(b -chloro-a -oxyethyl)-acrylic acid is mixed with urea- or melamine-formaldehyde resins in the presence of an acidic catalyst to provide a textile dressing.  In Example (15) a dioxane solution of poly - N - (b  - trichloro - a  - oxyethyl)-acrylic acid amide is mixed with a butanol solution of a butyl ether of methylol melamine and with HCl; a similar lacquer may be prepared from the similar polymethacrylic acid amide.  In Example (16) a dioxane solution of the addition polymer of Example (15) is mixed with an epoxy resin derived from epichlorhydrin and bisphenol A and with triethylene tetramine.