Patent GB-799951-A (GB)
Title: Improvements in or relating to mucilages and preparation thereof
IPC: C08F36/20
Filed: 1955-01-10
Abstract: Aqueous dispersions of salts of copolymers of unsaturated acids and polyunsaturated crosslinking agents are used in polishing compositions together with scouring and polishing agents such as pumice, diatomaceous earth, oily hydrocarbons, vegetable oils and wax solutions.  In an Example (11) a polish is made from the sodium salt of the methyl half-ester of a maleic anhydride/vinyl methyl ether/polyallyl sucrose copolymer, water, diatomaceous earth, kerosene and mineral oil.ALSO:Smooth non-grainy mucilaginous compositions are made by preparing a finely divided water-insoluble but water-sensitive copolymer by copolymerizing a mixture of monomers comprising at least 25 per cent of an olefinically unsaturated carboxylic acid or anhydride or acid halide and from 0.1 to 10 per cent, based on total polymerizable material of a cross-linking monomer containing a plurality of CH2 = C< or crotyl groupings, the polymerization being conducted in a liquid hydrocarbon or halogenated hydrocarbon which is a solvent for the monomeric mixture but having no swelling action on the resulting copolymer, e.g. benzene, toluene, xylene, hexane, heptane, methyl chloride, ethyl chloride, carbon tetrachloride and mixtures thereof, mixing the finely divided copolymer with water and sufficient of a monovalent base, e.g. sodium, potassium, lithium and ammonium hydroxides, carbonates, bicarbonates and oxides and amines, to neutralize from 10 to 85 per cent of the carboxyl groups in the copolymer, the resulting aqueous mixture containing 0.1 to 10 per cent of the copolymer salt, and grinding the neutralized copolymer in the aqueous mixture until a smooth non-grainy mucilaginous composition is obtained.  In one method of putting the process into effect a dry mixture of copolymer and base is prepared which is mixed with water when required.  Acid monomers specified are acrylic, methacrylic, ethacrylic, alpha-chloroacrylic, alpha-bromoacrylic, alpha-cyanoacrylic, alpha-phenylacrylic, alpha - benzylacrylic, alpha - cyclohexylacrylic, alpha- and beta-vinyl acrylic, alpha- and beta-styryl acrylic, crotonic, beta-acryloxy propionic, alpha, beta isopropylidene propionic, sorbic, cinnamic alpha-butyl crotonic, angelic, m- and p-chlorocinnamic, hydrosorbic, umbellic, maleic, itaconic, mesaconic, aconitic, glutaconic, muconic and hydromuconic acids, 3-carboxypentadiene - (2,4) - oic - 2, and maleic, chlormaleic and citraconic anhydrides.  Cross-linking monomers specified are divinyl benzene and naphthalene, low molecular weight polybutadiene, ethylene glycol diacrylate and dimethacrylate, glyceryl di- and tri-acrylates, allyl, methallyl and crotyl acrylates, diallyl oxalate, phthalate, maleate and malonate, diallyl allyl malonate, di- and tri-allyl citrates, alpha, beta-(2-propene) propionic acid, acrylic and methacrylic anhydrides, triacrylyl triazine, triallyl cyanurate, divinyl, diallyl and dimethallyl ethers, diallyl ethylene glycol ether, diallyl and triallyl glycerol ethers, diallyl 1,2-propanediol ether, diallyl 3-butene-1,2-diol ether, diallyl and triallyl ethers of 1-phenyl-1,2,3-propanetriol, diallyl 1,5 - naphthalenedimethylol ether, di-, tri- and tetra-allyl 1,4,5,8-naphthalene tetrol ethers, divinyl ketone, diallyl ketone, allyl betaallyloxy propionate, allylmethacrylyl sucrose, monoallyl maleate, hexa-allyl trimethylene sulphone and polyalkenyl polyethers of polyhydric alcohols, e.g. the allyl, methallyl and crotyl ethers of butane triols, erythritol, erythrose, threose, erythrulose, arabinose, xylose, lyxose, ribose, araboketose, xyloketose, glucose, galactose, mannose, idose, allose, fructose, sorbose, sucrose, maltose, lactose, raffinose, starch, xylitol, pentaerythritol, arabitol, mannitol, iditol, tallitol, sorbitol, inositol, dulcitol, acetylated sucrose, galactamine, glucosamine and fructosamine.  Part of the acid monomer may be replaced by other monomers such as vinyl acetate, vinyl chloracetate, vinyl benzoate, methyl acrylate, methyl alpha-chloroacrylate and alpha-cyanoacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, N-methylacrylamide, methacrylamide, vinyl and vinylidene chlorides, vinyl pyridine, carbazole and pyrrolidone, vinyl methyl, vinyl ethyl and vinyl n-butyl ethers, styrene, ethylene, isobutylene and diethyl maleate.  Polymerization may be effected in the presence of a catalyst, such as benzoyl peroxide, caprylyl peroxide or azobisisobutyronitrile, and by a process which involves the gradual addition of the monomers to the reaction vessel as the reaction proceeds.  The mucilages produced are used in making ointments, toothpastes, surgical jellies, bulk laxatives, ion-exchange resins, printing pastes and polishes.  In examples the following compositions are described: (2) a toothpaste consisting of the sodium salt of an acrylic acid/divinyl benzene copolymer, aqueous glycerol and calcium carbonate; (3) a toothpaste consisting of the sodium salt of an acrylic acid/polyallyl sucrose copolymer, sodium metaphosphate, calcium phosphate, aqueous glycerol and a sodium sulphonate surface-active agent; (9) a toothpaste as in (3) made from the sodium salt of a maleic anhydride/divinyl ether/polyallyl sucrose copolymer in which the divinyl ether cross-links have been hydrolysed; and (11) a polish made from the sodium salt of the methyl half-ester of a maleic anhydride/vinyl methyl ether polyallyl sucrose copolymer, water, diatomaceous earth, kerosene and mineral oil.ALSO:Aqueous dispersions of salts of copolymers of unsaturated acids and polyunsaturated cross-linking agents are used in toothpaste compositions.  In examples the following toothpaste compositions are described: (2) a mixture of the sodium salt of an acrylic acid/divinyl benzene copolymer, aqueous glycerol and calcium carbonate; (3) a mixture of the sodium salt of an acrylic acid/polyallyl sucrose copolymer, sodium metaphosphate, calcium phosphate, aqueous glycerol and a sodium sulphonate surface-active agent; and (9) a mixture of the sodium salt of a maleic anhydride/divinyl ether/polyallyl sucrose copolymer sodium metaphosphate, calcium phosphate, aqueous glycerol and a sodium sulphonate surface-active agent.