Patent GB-749801-A (GB)
Title: Improvements in or relating to emulsions of ionically crossed-linked resins and their use
IPC: C09D133/06
Filed: 1954-02-04
Abstract: Stable aqueous dispersions comprise a nonionic emulsifier, a water-insoluble copolymer containing in the molecule an ester of acrylic or methacrylic acid and 0.25 to 25 mol. per cent of carboxyl-containing units derived from acrylic, methacrylic, or itaconic acids, and a basic compound having at least a solubility in water of 0.0006 gms. per 100 c.c., in an amount from 0.125 to 12.5 mol. per cent based on the weight of copolymer, consisting of an oxide or hydroxide of barium, calcium, magnesium, or strontium, a hydroxide of aluminium, lead, or zirconium, or a weak acid or basic salt of a polyvalent metal such as the normal and basic acetates of barium, calcium, cadmium, cerium, strontium, zirconium, lead, cobalt (-ic and -ous), chromium (-ic and -ous), copper (-ic), zinc, magnesium, iron (-ous), manganese (-ous), mercury (-ic), and nickel (-ic and -ous), stannous tartrate, titanium oxalate, the basic acetates of aluminium and zirconium, and basic aluminium formate, the polyvalent metals serving to crosslink the copolymers ionically. Esters of acrylic and methacrylic acids specified are the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, isoamyl, tert.-amyl, hexyl, heptyl, n-octyl, and 2-ethylhexyl esters.  Also present in the copolymers may be units of other monoethylenically unsaturated compounds such as vinyl and vinylidene chlorides, styrene, vinyl toluene, vinyl naphthalene and lauryl, octadecyl, benzyl, and phenylethyl acrylates and methacrylates, the amount of such compounds present in the copolymer on a molar basis being less than the amount of ester.  Non-ionic emulsifiers specified are alkylphenoxypolyethoxyethanols such as the heptyl, octyl, methyloctyl, nonyl, and dodecyl phenoxypolyethoxyethanols, polyethoxyethanol derivatives of methylene-linked alkyl phenols, sulphur containing agents made by condensing ethylene oxide with nonyl, dodecyl, tetradecyl and t.-dodecyl mercaptans or with alkylthiophenols having alkyl groups of 6 to 15 carbon atoms, ethylene oxide derivatives of lauric, myristic, palmitic, oleic, and tall oil acids, ethylene oxide condensates with octyl, decyl, lauryl, and cetyl alcohols, the ethylene oxide derivative of sorbitan monostearate, and copolymers of ethylene and propylene oxides.  The copolymer dispersions are preferably obtained by copolymerizing the monomeric esters and acids in aqueous emulsion in the presence of a nonionic emulsifier.  Polymerization may be assisted by heat and catalysts such as combinations of oxidizing agents, e.g. alkali metal and ammonium persulphates and perborates, hydrogen peroxide, tert.-butyl hydroperoxide, cumene hydroperoxide, and tert.-butyl perbenzoate, and reducing agents such as sodium metabisulphite, sodium hydrosulphite, thiosulphates, and salts of metals capable of existing in more than one valence state such as cobalt, iron, nickel and copper. In one method of polymerization the reaction is carried out initially in the presence of a mixture of ammonium persulphate and sodium hydrosulphite at a temperature of up to 60 DEG  C. followed by cooling to 38 DEG  C. in an ice-bath and further polymerization in the presence of tert.-butyl hydroperoxide. The dispersions are used in the manufacture of films and coatings by coalescence of the copolymer particles, cross-linking occurring as water dries out.