Benzoyl peroxide treatment of reaction products of diisocyanates with linear polyesters

摘要

Organic diisocyanate modified polyesters and polyesteramides which may be unsaturated are cured by heating in the presence of a nitrocompound, a peroxide or a quinone oxime. Curing agents specified are benzoyl peroxide, quinone-dioxime, dinitrobenzene and trinitrobenzene. The amount of curing agents may be 1.0 to 5.0 parts per 100 parts of polymeric material. Additional ingredients specified are fillers, for example, iron oxide, clay, asbestos, blanc fixe and mica; other plastic materials, for example, synthetic rubbers, vulcanized vegetable oils, dark substitute, white substitute, wood rosin and pitch; detackifying agents, for example, stearic acid, paraffin wax, oleic acid and lauric acid; plasticisers, for example, tricresyl phosphate, dibutyl phthalate, butylphthalyl butyl glycollate and N-alkyltoluenesulphonamides; stabilisers or anti-oxidants, for example, hydroquinone, N : N1-hexamethylene - bis - o - hydroxybenzamide, N - phenyl - a - naphthylamine, N - phenyl - b - naphthylamine and a : a -bis-(2-hydroxy-3 : 5-dimethylphenyl-) butane, pigments, for example 1-3 per cent by weight, such as are customarily used in rubber technology. The ingredients are compounded at 70-90 DEG C., if desired in the presence of a solvent or swelling agent. The mix may be shaped or calendered on to a substrate and heated at 100-150 DEG C. The materials may be used in the construction of petrol- and/or oil-resistant articles of all kinds, for example gaskets, packings, hose, diaphragms for pumps and the like, in the fabrication of flexible containers, in the manufacture of rollers, blankets and stereos for use in the printing industry, to provide protective sheathings for insulated electric cables, in the construction of balls for games, tyres, elastic threads, conveyer or transmission belting, engine bearings, coated fabrics, including protective clothing and floor coverings, and generally in the construction of articles requiring the use of a material having physical properties resembling those of rubber, but also having a good resistance to the action of organic fluids and a low permeability to gases and vapours. Polyester and polyamide-forming reactants are ethylene glycol, diethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, dodecamethylene glycol, 1 : 12-octadecanediol and pentaglycol; aliphatic or aromatic aminoalcohols having at least one hydrogen atom attached to the amino nitrogen atom and preferably containing an aliphatic chain of at least two carbon atoms separating the amino and hydroxyl groups, for example b -ethanol-amine and 3-aminopropanol; dibasic carboxylic acids or ester-forming derivatives thereof, preferably aliphatic dicarboxylic acids, for example, malonic, succinic, glutaric, adipic, b -methyladipic, pimelic, suberic, azelaic, sebacic, undecanedioic, brassylic, iso-phthalic, hexahydroterephthalic, p - phenylenediacetic, and acetone-dicarboxylic acids; primary and secondary diamines, for example, ethylene diamine, hexamethylene - diamine, 3 - methylhexamethylene diamine, decamethylenedi - amine, m-phenylenediamine, N : N1-dimethylhexamethylenediamine, N : N1 - diethylhexa - methylenediamine and N : N1-dimethyldecamethylene - diamine; monohydroxymonocarboxylic acids or their ester-forming derivatives, for example, glycollic, 6-hydroxy-caproic, 10-hydroxydecanoic and 12-hydroxystearic acids; and polymerizable monoaminomonocarboxylic acids, or their ester-forming caprolactam, and 9-aminononanoic, 11-amino-undecanoic and 12-aminostearic acids; unsaturated dibasic carboxylic acids, or their ester-forming derivatives, for example, maleic, fumaric and dihydromuconic acids, acetylene dicarboxylic acid and itazonic acid; unsaturated aliphatic diamines, for examples, 1 : 4-diaminobutene; unsaturated glycols, for example, 1 : 4-butene diol. Suitable proportions of the reactants containing the unsaturated linkages are from 5 to 25 parts per 100 parts by weight of the total reactants. The polyesters and polyester-amides are made by usual methods, if desired, in the presence of a polymerization inhibitor such as hydroquinone, copper powder or copper rosinate. Diisocyanates specified are ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p : p1-diphenyl diisocyanate and naphthalene diisocyanates. In examples, the organic diisocyanate-modified unsaturated polyester prepared as described in example 1 of Specification 573,811 is compounded with stearic acid, ferric oxide and benzoyl peroxide, and the product moulded and heated. Dinitrobenzene or quinone dioxime may be used instead of benzoyl peroxide and the organic diisocyanate modified polyester-amide obtained from adipic acid, maleic acid, ethylene glycol, b -ethanolamine, and hexamethylene diisocyanate may be used. Specification 580,524 also is referred to.