Patent GB-814721-A (GB)
Title: New quaternary ammonium compounds and their manufacture and use
IPC: C08G59/50
Filed: 1955-05-25
Abstract: Water-soluble quaternary ammonium compounds containing at least two quaternary nitrogen atoms to each of which are bound one epoxy-propyl group and one or two hydroxyethyl or hydroxy (mono- or poly-ethoxy) ethyl groups, obtained as hereinafter specified, may be used for the manufacture of compositions suitable for moulding under pressure and shaped bodies, films or adhesive agents by using them in conjunction with compounds capable of reacting with epoxy groups; they also may be used for the cross-linking of unspecified polymerization or condensation products.  The quaternary compounds are those produced by reacting epichlorhydrin under substantially anhydrous conditions with the addition products of 2 molar proportions of ethylene oxide and 1 molar proportion of piperazine or a diacylated triethylene tetramine in which the acyl radicals are derived from a C12-18 fatty acid, or of 4-15 molar proportions of ethylene oxide and one molar proportion of ethylene diamine, trimethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetra ethylene pentamine or a trimethylene diamine having one C12-18 alkyl group bound to nitrogen, the molar proportions of ethylene oxide in the stated range being at least equal to the number of amino hydrogen atoms in the polyamine, or the addition product of 4 molar proportions of ethylene oxide and 1 molar proportion of N : N1-di-(b -cyano ethyl) diethylene triamine in which addition product one hydroxyl group is esterified with a C12-18 fatty acid, the amount of epichlorhydrin used in each reaction being sufficient to quaternize at least two tertiary amino nitrogen atoms (see Group IV (b)).ALSO:New water-soluble quaternary ammonium compounds containing at least two quaternary nitrogen atoms to each of which is bound one epoxy-propyl group and one or two hydroxyethyl or hydroxy-(mono- or poly-ethoxy)-ethyl groups are prepared by reacting epichlorhydrin under substantially anhydrous conditions with the addition products of 2 molecular proportions of ethylene oxide and one molecular proportion of piperazine or a di-acylated triethylene tetramine in which the acyl radicals are derived from a fatty acid having 12 to 18 carbon atoms, or of 4-15 molecular proportions of ethylene oxide and one molecular proportion of ethylene diamine, trimethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or a trimethylene diamine containing one alkyl radical having 12-18 carbon atoms and bound directly to a nitrogen atom, the molar proportions of ethylene oxide in the specified range being at least equal to the number of amino hydrogen atoms in the polyamine, or the addition product of 4 molecular proportions of ethylene oxide and one molecular proportion of N : N1-di-(b -cyanoethyl) diethylene triamine in which addition product one hydroxy group is esterified with a fatty acid containing 12 to 18 carbon atoms, the amount of epichlorhydrin used in each of the above reactions being sufficient to quaternize at least two tertiary amino nitrogen atoms.  The quaternation is preferably effected at raised temperature, for example, 70 DEG -120 DEG  C., and advantageously in an inert atmosphere; an inert solvent may be present.  The quaternary ammonium compounds may be used in bringing about crosslinking in certain polymerization or condensation products and can be used in conjunction with compounds capable of reacting with epoxy groups to form mouldable compositions and shaped bodies, films or adhesives. Some may also be used as assistants in the textile, leather and paper industries.  They may be used for imparting an anti-electrostatic effect to fibrous materials, for imparting a soft feel to various fibrous materials and for impregnating or coating glass fibres (see Group IV (c)).  In examples: (1) a mixture of N-mono-C16-18-alkyl trimethylene diamines is reacted with 7 molar proportions of ethylene oxide and the product is di-quaternized with epichlorhydrin by heating in a current of nitrogen on a waterbath and is thereafter stripped of volatile constituents and any unchanged starting materials present are extracted with acetone; (2) triethylene tetramine is di-acylated with stearic acid at 140-145 DEG  C., water of reaction being removed in a current of nitrogen and the diamide is then reacted with 2 moles. of ethylene oxide; the product containing two tertiary amino nitrogen atoms is then di-quaternized as in (1); (3) diethylene triamine is reacted with 2 moles. of acrylonitrile, the resulting N : N1-di-(b -cyanoethyl)-diethylene triamine is condensed with 4 moles. of ethylene oxide, the N-hydroxy-ethylated product is reacted with stearic acid in a current of N2 at 160-165 DEG  C. and the monoester formed is tris-quaternated with epichlorhydrin as in (1); (4) piperazine is reacted with ethylene oxide to form N : N1-di-hydroxy ethyl piperazine which is di-quaternized with epichlorhydrin; the product may be purified by chloroform extraction; (5) the reaction product of ethylene diamine with 4 moles. of ethylene oxide is di-quaternized with epichlorhydrin and purified by extraction with acetone; (6)-(8) diethylene triamine is condensed with 15 moles. of ethylene oxide, triethylene tetramine is reacted with 6 moles. of ethylene oxide and tetraethylene pentamine is reacted with 7 moles. of ethylene oxide and the products are then reacted with epichlorhydrin as in (1) yielding ammonium compounds containing at least two quaternary nitrogen atoms; the products are purified by extraction with acetone or chloroform.ALSO:Water-soluble quaternary ammonium compounds containing at least two quaternary nitrogen atoms to each of which are bound one epoxypropyl group and one or two hydroxyethyl or hydroxy (mono- or poly-ethoxy)-ethyl groups, obtained as described hereinafter, may be used for producing impregnations in or coatings on glass fibres or threads or materials produced therefrom, for imparting a soft feel to cellulose, polyamide or polyacrylonitrile fibres and for imparting an anti-electrostatic effect to fibrous materials.  The quaternary compounds are those prepared by reacting epichlorhydrin under substantially anhydrous conditions with the addition products of 2 molar proportions of ethylene oxide and 1 molar proportion of piperazine or a diacylated triethylene tetramine in which the acyl radicals are derived from C12-18 fatty acids or of 4-15 molar proportions of ethylene oxide and 1 molar proportion of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexamethylene diamine, trimethylene diamine or an N-mono C12-18 alkyl trimethylene diamine, the molar proportions of ethylene oxide in the stated range being at least equal to the number of amino hydrogen atoms in the polyamine, or the addition product of 4 molar proportions of ethylene oxide and 1 molar proportion of N : N1 - di - (b  - cyanoethyl) - diethylene triamine in which addition product one hydroxyl group is esterified with a C12-18 fatty acid, the amount of epichlorhydrin used in each reaction being sufficient to quaternize at least 2 tertiary amino nitrogen atoms (see Group IV (b)).  In examples, (9) artificial silk is given a soft feel by treatment in a bath comprising a diquaternary ammonium compound prepared as above described from a mixture of N-mono C16-18 alkylated trimethylene diamines; (10) a yarn of hexamethylene diamine adipic acid polyamide is similarly treated in a bath comprising triethylene tetramine and a di-quaternary compound prepared as above described from piperazine, whereby its electrical conductivity is improved; (11) polyacrylonitrile yarn is given a similar effect using a bath comprising triethylene tetramine and a product obtained as described above from triethylene tetramine and containing at least two quaternary nitrogen atoms.  Several other quaternary compounds of the type specified are described.