Patent GB-903972-A (GB)
Title: Copolymers and their production
IPC: C08F36/00
Filed: 1960-03-16
Abstract: Copolymers comprising 65 to 99 mole per cent of a first recurrent group having the structure <FORM:0903972/IV(a)/1> where R is hydrogen or an alkyl radical having 1 to 8 carbon atoms and 35 to 1 mole per cent of at least one second recurrent group having the structure <FORM:0903972/IV(a)/2> , <FORM:0903972/IV(a)/3> , <FORM:0903972/IV(a)/4> , <FORM:0903972/IV(a)/5> , <FORM:0903972/IV(a)/6> , <FORM:0903972/IV(a)/7> , <FORM:0903972/IV(a)/8> or <FORM:0903972/IV(a)/9> where Z i a monovalent sulphate, halogen, thioalkyl, thioaryl or thioaryl carboxylic acid radical; X and Y are hydroxyl, acyloxy, nitrite or nitroso radicals wherein X and Y may be the same when they are hydroxyl radicals and are dissimilar in all other cases, and the nitrite and nitroso groups are mutually exclusive of each other; may be prepared by copolymerizing 1 to 35 mole per cent of propadiene with 99 to 65 mole per cent of a terminally unsaturated olefin and reacting the resulting copolymer with an active hydrogen containing agent or oxidizing agent.  Copolymerization may be effected in the presence of catalysts comprising mixtures of compounds of Group IVa, Va or VIa metals, iron, cobalt, copper, nickel or manganese, the metal having attached thereto halogen, oxygen, hydrocarbon or oxyhydrocarbon, with hydrides or organo compounds of metals of Group I, II or III, many suitable catalyst components being listed. Copolymerization may be effected in liquid media, e.g. hexane, benzene, toluene, cyclohexane, bromobenzene, chlorobenzene, o-dichlorobenzene, tetrachloroethylene, dichloromethane, 1,1,2,2-tetrachloroethane, p  tetrahydrofuran, thiophene and dioxane. Specified active hydrogen containing agents are sulphuric acid, sulphurous acid, chlorosulphonic acid, thiosulphuric acid, pyrosulphuric acid, para-toluene sulphonic acid, salicylic acid, meta-hydroxybenzoic acid, parahydroxybenzoic acid, hydrogen sulphide, ethanethiol, 1-propanethiol, 2-propanethiol, 1-hexanethiol, 1-decanethiol, benzenethiol, thiosalicylic acid, mercaptobenzothiazole, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide. Specified oxidizing agents are percarboxylic acids, hydrogen peroxide, potassium permanganate, alkaline hypochlorites, oxides of nitrogen, chromic acid, nitric acid, periodic acid, oxides of osmium, vanadium, chromium, selenium and silver, hypobromous acid, hypochlorous acid, lead tetraacetate, chromyl chloride, mercury salts, oxygen and ozone.  The reaction with the copolymer may be carried out in the presence of aqueous, organic or mixed aqueous/organic solvent systems.  Reaction with the active hydrogen containing agent may be effected in the presence of a catalyst, e.g. azodiisobutyronitrile or aluminium chloride. Examples describe the copolymerization of ethylene and propadiene in the presence of vanadyl trichloride and aluminium triisobutyl and the reaction of the copolymer with (1) 1-propanethiol in the presence of azodiisobutyronitrile; (2) benzenethiol in the presence of azodiisobutyronitrile; (3) thiosalicylic acid in the presence of azodiisobutyronitrile; (4) hydrogen fluoride; (5) hydrogen bromide; (6 to 15) sulphuric acid; and (16) salicylic acid in the presence of aluminium chloride; the copolymerization of 1-hexene and propadiene in the presence of vanadyl trichloride and aluminium triisobutyl and the reaction of the product with (17) hydrogen bromide; and the reaction of copolymers of ethylene and propadiene with (18, 19, 28, 29 and 30) peracetic acid; (20) calcium hypochlorite; (21 and 25) hydrogen peroxide; (22) a mixture of potassium dichromate and concentrated sulphuric acid; (23) nitrogen tetroxide; (24) potassium permanganate; (26) peracetic acid and thereafter with propanethiol; and (27) peracetic acid and thereafter with salicylic acid.  The products are useful in the manufacture of films, foils, filaments, fibres, rods and tubes.