Patent GB-779232-A (GB)
Title: Manufacture and use of polymerisable or co-polymerisable amide-like compounds
IPC: C07G99/00
Filed: 1953-08-27
Abstract: Amide-like polymerizable or copolymerizable products are prepared by reacting (a) a methylol compound of the amino-1 : 3 : 5-triazine or urea group, as hereinafter defined, containing at least two free methylol groups, or an ether thereof with an aliphatic alcohol having at most 4 carbon atoms; with (b) a nitrile or amide of an unsaturated polymerizable or copolymerizable acid, the amide containing hydrogen attached to amido nitrogen, in the presence of an acid condensing agent, if necessary at a raised temperature, and additively combining the condensation product so obtained with (c) a compound capable of additive combination at a double bond, namely, an alcohol, phenol, mercaptan, a primary or secondary amine or an alkali metal bisulphite, the proportions of the reaction components being such that the final product contains at least one unsaturated residue derived from component (b) which renders the product polymerizable or co-polymerizable.  In a modification, the reactant (a) is capable of having further methylol groups introduced into it and after its condensation with reactant (b) the product is reacted with formaldehyde and then with reactant (c), the final product still being characterized by having at least one unsaturated residue derived from component (b).  The methylol compounds of the amino-1 : 3 : 5-triazine group are the methylol compounds of melamine, which contain 2-6 methylol groups, of melamine derivatives containing at least one amino group such as melam, melem, ammeline, ammelide or halogen-substituted amino triazines such as 2-chloro-4:6-diamino-1:3:5-triazine and of guanamines, e.g. benzo-guanamine, aceto-guanamine and formo-guanamine, and the methylol compounds of guanyl melamines, including mono-, di- and tri-guanyl melamines, obtainable as described in Specification 730,018 and of substituted guanyl guanamines.  The ethers of these methylol compounds which may be used may be derived from methanol, ethanol, propanols and butanols and include methyl ethers of methylol melamines containing 3-6 methylol groups of which 2 or more are etherified.  The amino-triazine methylol compounds and their ethers may contain such substituents as ester, amide or further ether groups.  The methylol compounds may be used in partially condensed condition.  The methylol compounds of the urea group are the methylol group containing condensation products from at least 2 mols. of formaldehyde and 1 mol. of urea, thiourea or a non-cyclic compound containing the atomic grouping: <FORM:0779232/IV(a)/1> such as dicyandiamide, dicyandiamidine, guanidine, aceto guanidine and biguanide.  The unsaturated nitriles and amides may be derived from acyclic or homo- or hetero-cyclic mono- or polycarboxylic acids containing at least one double or triple bond.  The preferred nitriles and amides are derived from the acids: <FORM:0779232/IV(a)/2> where R represents H, Cl or an alkyl group but others mentioned include the dinitriles of muconic acid and acetylene dicarboxylic acid and the nitriles of cinnamic, furylacrylic and crotonic acids.  The reaction of the nitriles or amides with the reactants (a) may be carried out in an inert solvent.  When a nitrile is condensed the condensing agent may be used in a molar excess. Specified condensing agents are the strong mineral acids.  The additive combination of the condensation product with reactant (c) is effected in known manner for the addition of such compounds to a double bond; that with alcohols, phenols or mercaptans is generally carried out in the presence of a small amount of a strongly alkaline catalyst, e.g. alkali metal hydroxides or alcoholates; condensation with the alkali metal bisulphites and most of the amines is carried out in the absence of such a catalyst.  Inert solvents may be present.  Numerous examples of reactant (c) are given including methanol, allyl alcohol, tertiary butanol, p-tolyl carbinol, tetra-hydro naphthyl carbinols, 2-oxythiazole, oxyethane sulphonic acid, phenol, 2:4-dichlorphenol, p-bromophenol, guaiacol, amyl mercaptan, allyl mercaptan, thioglycollic acid, thioethylene glycol, thiophenol, 2-mercapto thiazoline, methylamine, propanolamines, polyalkylene polyamines, alanine, taurine, N-methyl cyclohexylamine, benzylamine, naphthylamines, chloraniline, piperidine, pyrrolidine, benzimidazole and tetrahydro-quinoline.  The products derived from the condensation products prepared by the above-mentioned modification are heathardenable.  Such products are also obtainable when reactant (a) is heat-hardenable and the reactants are used in such proportions that the final product contains at least one free methylol group.  The amide-like final products may be polymerized including co-polymerized in bulk, solution or emulsion using heat, actinic light or one of the usual polymerization catalysts, e.g. inorganic or organic peroxides, many of which are mentioned. Regulators such as mercaptans or terpenes and activators such as SO2, sodium bisulphite, sulphite, hydrosulphite and thiosulphate, triethanolamine, diethyl - ethanolamine, complex cyanides of Fe, Co, Mo, Hg, Zn, Cu or Ag, or a multi-valent heavy metal compound in the reduced condition, may be present.  Numerous emulsifying agents are specified which may be used with protective colloids; alternatively the colloids may be used as emulsifying agents. Polymerization may be effected in solvents in which the polymer may or may not be soluble. Polymerization temperatures are generally from 40 DEG  to 95 DEG  C. Softening agents or organic or inorganic pigments or fillers may be added.  Polymerization or copolymerization and, if desired, hardening may be effected on a fibrous substrata, e.g. a textile material, the latter being thereby waterproofed.  If the amide-like products are hardenable, they may be polymerized with simultaneous or subsequent hardening; catalysts may be used such as hydrochloric, sulphuric or formic acid; ammonium chloride, sulphate, nitrate oxalate or lactate, acetic acid, chloracetic acid, diethyl tartrate and triacetin. Co-polymerization of the amide-like products of the invention may be effected with, for example, vinyl acetate, formate, butyrate or benzoate; vinyl alkyl ketones; vinyl chloride or fluoride or vinylidene chloride; styrene and substituted styrenes; ethyl, butyl or dodecyl acrylates, acrylamide and acrylonitrile and analogous derivatives of methacrylic, chloracrylic, crotonic, maleic and fumaric acids; acrylic and methacrylic acids; isobutylene, butadiene and 2-chlorobutadiene.  The products may be used to prepare films, adhesives and lacquers and also as textile assistants (see Group IV (c)).  In typical examples: (1) a water-soluble trimethylol melamine is stirred into 93 per cent H2SO4 and then acrylonitrile (ca. 2 mols.) is added dropwise at up to 35 DEG  C.; the resulting condensation product is isolated and is reacted with diethylamine in ethylene glycol monoethyl ether at up to 100 DEG  C., the product being an oil, soluble in aqueous acid; (3) a partially insoluble trimethylol melamine (preparation given) is similarly condensed with acrylonitrile (ca. 3 mols.) at 0-10 DEG  C. and the resulting product, which is polymerizable in aqueous solution, is isolated and reacted with ethylene diamine in pyridine and the product recovered in the form of its acetate salt which yields salts with acid-dyestuffs; a similar product is obtained when diethylene triamine is used as the amino reactant; (5) the preparation is described of a number of condensation products from reactants (a) and (b) for use in reaction with organic reactant (c) including those obtained from (i) hexamethylol melamine and acrylonitrile (3 mols.), (ii) trimethyl ether of partially condensed trimethylol melamine and acrylonitrile (2 or 3 mols.), (iii) a partially condensed hexamethylol melamine n-butyl ether containing about 4 butoxy groups and acrylonitrile (3 mols.), and (iv) from dimethylol melamine and acrylonitrile (2 mols.), this condensate thereafter being reacted with formaldehyde in aqueous alkali to yield a watersoluble product which is itself polymerizable; (7) the condensation product of 5 (iv) is additively combined with diethylamine in ethylene glycol monoethyl ether by heating up to 90 DEG  C. and the product is quaternated with benzyl chloride; the quaternated product so formed in aqueous solution may be polymerized by addition of potassium persulphate, and also yields an insoluble resin on addition of an aqueous polyacrylic acid solution; and (8) may be copolymerized with acrylamide; (9) the condensation product of 5 (iv) is heated with hexadecyl mercaptan in ethylene glycol monoethyl ether and methanolic KOH yielding an insoluble mass which is either polymerized on treating in alcoholic ethylacetate solution with benzoyl peroxide or (20) copolymerized with n-butyl acrylate; (10) the condensation product of 5 (iv) is heated with trimethylene diamines R.NH. CH2CH2CH2NH2 (R = alkyl radicals corresponding to soya bean oil acids) in ethylene glycol monoethyl ether yielding an insoluble oil; the oil is dissolved in aqueous acetic acid and polymerized to an insoluble polymer by potassium persulphate; (11)-(16) analogous monomers and polymers are obtained when the amines of (10) are replaced by morpholine, piperidine, diethanolamine, aniline, phenol and dibutylamine; (17) the condensation product of 5 (iv) is reacted as in (10) with diethylamine and the product is quaternated with methylol chloracetamide yielding a solution from which a resin is precipitated on addition of either potassium permanganate or an aqueous solution of polyacrylic acid; also the quaternated compound is copolymerized by heating with acrylamide using potassium persulphate catalyst; (18) the condensation product of 5 (iv) is refluxed with an aqueous-alcoholic solution of NaHSO3; the resulting soluble product is polymerized by means of potassium persulphate.