Verfahren zur Herstellung von Acrylnitrilmischpolymerisaten

摘要

Copolymers are prepared from a mixture comprising (1) acrylonitrile, and (2) one or more quaternary ammonium compounds represented by the general formula [Z-R]+X-where Z represents a tertiary amino grouping, R represents an ethylenically unsaturated hydrocarbon radical having a terminal group containing from 3 to 10 carbon atoms, and X - represents an anion, the amount of compound (2) constituting from 1 to 15 per cent. of the total amount of (1) and (2). Compounds specified are allyltriethylammonium chloride and bromide, allylpyridinium chloride and bromide, methallylpyridinium chloride, allyldimethylphenylammonium bromide, and allyl-bis-(2-hydroxyethyl) methylammonium chloride and bromide; also listed are other tertiary amino groupings, unsaturated hydrocarbon radicals, and anions including phosphate, borate, and silicate. Other copolymerizable monomers may be present in the reaction mixture such as styrene, dialkyl styrenes, and isopropenyl toluene, vinyl acetate, propionate, butyrate, isobutyrate, valerate, acrylate, and methacrylate, acrylic, methacrylic, ethacrylic, and phenylacrylic acids and their ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.-butyl, amyl, hexyl, heptyl, octyl, decyl, and dodecyl esters, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, methacrylamide, ethacrylamide, N-monomethyl, N- monoethyl, N-monopropyl, N-monobutyl, N-dimethyl, N-diethyl, N-dipropyl, and N-dibutyl acrylamides and methacrylamides, N-methylol acrylamide, and N-monophenyl, and N-diphenyl acrylamides and methacrylamides. Polymerization may be carried out in bulk, in solution in solvents such as benzene, toluene, and xylene, or, preferably, in aqueous media at acid or alkaline pH, if desired by bead polymerization methods, and may be assisted by heat, light, and catalysts such as hydrogen, barium, and magnesium peroxides, ethyl, propyl, lauryl, oleyl, stearyl, tert.-butyl, and tert.-amyl peroxides, tert.-butyl, tert.-amyl, and cumene hydroperoxides, acetyl, propionyl, lauroyl, stearoyl, malonyl, succinyl, phthaloyl, and benzoyl peroxides, coconut oil peroxides, acetyl benzoyl peroxide, propionyl benzoyl peroxide, ascaridole, methyl ethyl ketone peroxide, sodium, potassium, and ammonium persulphates which may be used in conjunction with sodium metabisulphite, sodium and potassium perborates, percarbonates, and perphosphates, "Tetralin" (Registered Trade Mark) hydroperoxide, tert.-butyl perphthalate and perbenzoate, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, urea peroxide, caprylyl peroxide, 2, 2-bis (tert-butylperoxy) butane, hydroxyheptyl peroxide, the diperoxide of benzaldehyde, alpha, alpha1-azodiisobutyronitrile, and cobalt naphthenate. The copolymers may be formed into fibres susceptible to dyeing with acid dyes by the process described in Specification 695,449, from solution in organic solvents or aqueous solutions of sodium and calcium thiocyanates. The copolymers may also be used in moulding compositions in conjunction with fillers such as alpha-cellulose pulp, asbestos fibres, cotton flock, chopped cloth cuttings, glass fibres, wood flour, antimony oxide, titanium dioxide, sand, clay, mica dust and diatomaceous earth, and in adhesives and coating compositions.ALSO:Quaternary ammonium compounds represented by the general formula [Z-R]+X-, where Z represents a tertiary amino grouping, R represents an ethylenically unsaturated hydrocarbon radical having a terminal grouping containing from 3 to 10 carbon atoms, and X- represents a chloride or bromide ion, are prepared by mixing approximately equal amounts of an ethylenically unsaturated chloride or bromide with a tertiary amine along with an inert diluent, e.g. benzene, and heating to 25 DEG to 100 DEG C. for 1/2 to 10 hours, followed by filtration, washing, and drying of the precipitated quaternary ammonium compound. In examples the preparation is described of allyltriethylammonium chloride and bromide, allylpyridinium chloride and bromide, methallylpyridinium bromide, allyldimethylphenylammonium chloride, and allyl-bis-(2-hydroxyethyl) methylammonium chloride and bromide. Specification 695,449, [Group IV (a)], is referred to.