Patent GB-779231-A (GB)
Title: Manufacture and use of amide-like polymerisable or copolymerisable compounds
IPC: C07G99/00
Filed: 1953-08-27
Abstract: Amide-like polymerizable or copolymerizable compounds are prepared by reacting a methylol compound of the amino-1 : 3 : 5-triazine or urea group (as defined hereinafter), or an ether thereof with an aliphatic alcohol having at most 4 carbon atoms, with a nitrile of an unsaturated polymerizable or copolymerizable acid in the presence of an acid condensing agent, if necessary at a raised temperature (see also Group IV (b)).  The methylol compounds of the amino-1 : 3 : 5-triazine group are the methylol group-containing formaldehyde condensation products of melamine which may contain 1 to 6 methylol groups; the methylol compounds of melamine derivatives containing at least one amino group such as methylol compounds of melam, melem, ammeline, ammelide or halogen-substituted amino-triazines such as 2-chloro - 4 : 6 - diamino - 1 : 3 : 5 - triazine; methylol compounds of guanamines, e.g. benzo guanamine, aceto-guanamine or formo-guamine; and the methylol derivatives of guanyl and substituted guanyl-melamines such as are obtainable as described in Specification 730,018.  The ethers of these compounds which may be used may be derived from methyl, ethyl, propyl or butyl alcohols, for example, the methyl ethers of methylol melamines containing 3 to 6 methylol groups, 2 to 6 of which are thus etherified.  The aminotriazine methylol compounds and their specified ethers may contain further substituents, e.g. ester, amide or further ether groups.  The aminotriazine methylol compounds and their lower aliphatic ethers may be used in the monomeric or partially condensed condition.  The methylol compounds of the urea group are those methylol group-containing condensation products of formaldehyde with urea, thiourea or compounds containing the grouping: <FORM:0779231/IV(a)/1> in non-cyclic form such as dicyandiamide, dicyandiamidine, guanidine, aceto guanidine or biguanide.  The unsaturated nitriles employed may contain double or triple bonds and may be acylic, homocyclic or heterocyclic; specified nitriles are those of acrylic, methacrylic, furyl acrylic, crotonic, cinnamic, muconic, acetylene dicarboxylic, phenyl-propiolic and a -chloracrylic acids.  The amide-like condensation products may be polymerized to give rubber-like materials, films, adhesives or lacquers and may be used in the textile, leather and paper industries. Products capable of being hardened when heated to elevated temperatures are obtained when the amino triazine or urea group reagent is itself capable of being heat-hardened and is reacted with the nitrile in such proportion that the amide-like product contains at least one free methylol group or a C1-4 aliphatic ether thereof.  Heat-hardenable products are also obtained by reacting the amide-like products with formaldehyde to re-introduce methylol groups.  The newly introduced methylol groups may be reacted with an alcohol, ester, amide or N-methylol amide to further modify the properties of the amide-like products. Polymerization and copolymerization of the amide-like products may be carried out in bulk, solution or emulsion, using heat, actinic light or one of the usual polymerization catalysts, e.g. organic-peroxides, percarbonates, persulphates, perborates and hydrogen peroxide. Regulators such as mercaptans and terpenes and activators such as SO2 and sodium sulphite, bisulphite, hydrosulphite and thiosulphate, triethanolamine, diethyl-ethanolamine and complex cyanides of Fe, Co, Mo, Hg, Zn, Cn or Ag or a multi-valent heavy metal compound used in the reduced condition.  When emulsion-polymerization is employed there may be used as an emulsifying agent a fatty alcohol acid sulphate, sulphonated castor oil, a -oxy-octadecane sulphonate, sodium dioctyl sulpho-succinate, octadecylamine acetate, diethylcyclohexylamine dodecyl sulphate, oleyl amido ethyl-diethylamine acetate, cetyldimethyl-benzyl ammonium chloride, cetyl trimethyl ammonium bromide, p-trimethyl-ammonium-benzoic acid cetyl ester metho-sulphate, cetyl-pyridinium metho-sulphate, octadecyltrimethyl ammonium bromide, triethanolamine tristearate quaternized by diethyl sulphate, reaction products of cetyl, oleyl or octadecyl alcohol with 15-30 mols. of ethylene oxide, octyl-phenol polyglycol ethers and their sulphate esters, glycerine monolaurate or sorbitol monolaurate; the emulsifying agents may be used in admixture with protective colloids such as alginates, tragacanth, agar-agar, polyvinyl alcohols, partially esterified polyvinyl esters, glue, gelatine, dextrin, cellulose ethers and polyethylene oxides; alternatively the protective colloids may be used alone. Polymerization in solution may be effected in solvents in which the polymer is soluble or insoluble.  The polymerizations are preferably effected at 40-95 DEG  C.  The monomeric compounds may be polymerized or copolymerized and if desired hardened on fibrous substrata; in this connection, textile materials may be rendered water-repellent. Softening agents or organic or inorganic pigments or fillers may be added. When the monomeric amide-like products are hardenable, they may be polymerized and subsequently or simultaneously hardened.  The amide-like monomeric products may be polymerized with, for example, vinyl-acetate, formate, butyrate or benzoate; vinyl alkyl ketones; vinyl chloride, vinyl fluoride, vinylidene chloride; styrene and substituted styrenes; ethyl butyl or dodecyl-acrylate; acrylonitrile and acrylamide; a -chloracrylic, crotonic, maleic, fumaric, acrylic or methacrylic acid; isobutylene, butadiene, 2-chlorobutadiene or heterocyclic compounds containing at least one vinyl group.  In typical examples: (1) melamine is heated at about 80 DEG  C. with aqueous formaldehyde (3 mols.) at pH 8-9 until 1 part of the product just produces turbidity in 3-4 parts of cold water; the resulting trimethylol melamine of limited solubility is added with acrylonitrile (about 3 mols.) to 93 per cent sulphuric acid at 0-10 DEG  C. and a light fabric is foularded with a solution of the product in aqueous alcohol containing ammonium persulphate and heated to 120 DEG  C. whereby polymerization and condensation takes place in the fibre and the resulting dressing is fast to boiling; (4) hexa methylol melamine is similarly reacted with 3 mols. of acrylonitrile; and (14) the product is emulsified in water, potassium persulphate is added to initiate polymerization and thereafter more of the product is added so yielding a benzene insoluble polymer; (9) dimethylol urea is reacted with about 2 mols. of acrylonitrile (sulphuric acid as condensing agent) in methanol or ethanol and the product is polymerized by addition of potassium persulphate.  Specification 779,232 also is referred to.ALSO:Amido-like polymerizable or copolymerizable compounds are prepared by reacting a methylol compound of the amino-1 : 3 : 5-triazine or urea group (as defined hereinafter) or an ether thereof with an aliphatic alcohol having at most 4 carbon atoms, with a nitrile of an unsaturated polymerizable or copolymerizable acid in the presence of an acid condensing agent, if necessary at a raised temperature.  The methylol compounds of the amino-1 : 3 : 5-triazine group are the methylol group-containing formaldehyde condensation products of melamine which may contain 1 to 6 methylol groups; the methylol compounds of melamine derivatives containing at least one amino group such as methylol compounds of melam, melem, ammeline, ammelide or halogen-substituted amino-triazines such as 2-chloro-4 : 6-diamino-1 : 3 : 5-triazine; methylol compounds of guanamines, e.g. benzo guanamine, aceto-guanamine or formoguanamine; and the methylol derivatives of guanyl and substituted guanyl-melamines such as are obtainable as described in Specification 730,018.  The ethers of these compounds which may be used may be derived from methyl, ethyl, propyl or butyl alcohols.  The amino-triazine methylol compounds and their specified ethers may contain further substituents, e.g. ester, amide or further ether groups.  Thus the ester-like compounds may be obtained from polymethylolmelamines (or the lower ethers thereof) by partially esterifying with a high molecular weight aliphatic carboxylic acid or a cycloaliphatic or aromatic acid and several acids of these types are mentioned: the compounds containing further ether groups may be obtained similarly by partially etherifying with high molecular weight aliphatic alcohols or araliphatic alcohols including octyl, oleyl, octadecyl and benzyl alcohols; and the compounds containing amido-substituents may be derived from the polymethylol melamines or the ethers thereof and amides or N-methylol amides of the above-mentioned acids.  The amino-triazine methylol compounds and their lower aliphatic ethers may be used in the monomeric or partially condensed condition.  The methylol compounds of the urea group are those methylol group-containing condensation products of formaldehyde with urea, thiourea or compounds containing the grouping: <FORM:0779231/IV(b)/1> in non-cyclic form such as dicyandiamide, dicyandiamidine, guanidine, aceto guanidine or biguanide.  The unsaturated nitriles employed may contain double or triple bonds and may be acylic, homocyclic or heterocyclic; specified nitriles are those of acrylic, methacrylic, furyl acrylic, crotonic, cinnamic, muconic, acetylene dicarboxylic, phenyl-propiolic and a -chloracrylic acids.  The acid condensing agents are preferably strong inorganic acids and desirably the condensing agent is used in excess of a molar proportion.  Inert organic solvents, e.g. tetrahydrofurane or glacial acetic acid may be present.  The amide-like condensation products may be polymerized (see Group IV (a)). Products capable also of being hardened when heated to elevated temperatures are obtained when the amino triazine or urea group reagent is itself capable of being heat-hardened and is reacted with the nitrile in such proportion t