Cross-linking of polymers of fluoroolefins with amines

摘要

A cross-linked "at least half-halogenated" polymer containing fluorine and a plurality of saturated carbon chains bonded to each other by linkages where R is a polyfunctional organic radical, A is hydrogen or a monofunctional organic radical and n is an integer of at least 2 are made by reacting the polymer, e.g. by heating with a compound of the formula optionally in the presence of an inorganic base. The term "at least half-halogenated" means substitution in the polymer molecule by halogen atoms of at least half of the possible positions for such substitution. Polymers mentioned are homopolymers of 2-chloroperfluoropropylene, chlorotrifluoroethylene, bromotrifluoroethylene, dichlorodifluoroethylene, trifluoroethylene, and chlorofluoroethylene, copolymers of mixtures of these monomers, and copolymers of the monomers with ethylene, vinylidene fluoride, tetrafluoroethylene, perfluoropropylene, acrylic acid or acrylonitrile. The cross-linking agent may be mixed mechanically with rubbery polymers, dissolved in a common solvent for the polymer and cross-linking agent and the solvent removed, or incorporated in the latex of emulsion polymers prior to coagulation, or by the direct action of the cross-linking agent under pressure on thin sections of the polymer. Specified cross-linking agents are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexamethylene diamine, piperazine, 1,5-naphthalene diamine, diaminoanisole, diaminobenzoic acid, diamine stilbene, diaminotriphenylmethane, triamino-triphenylmethane, diaminophenol, tetramino 3,3 - dimethyldiphenyl-methane, diaminobenzene, triaminobenzene, triaminobenzoic acid, triaminophenol, 1,2-propylenediamine and 1,2,3-triaminopropane. Inorganic basic compounds mentioned are lead oxide, magnesium oxide, and zinc oxide. The cross-linked polymers may be in the form of films, sheets, coatings for wires, yarns and fabrics made of asbestos, glass, synthetic resins and natural fibres. The preparation of copolymers of chlorotrifluorethylene and vinylidene fluoride by bulk and aqueous suspension polymerization techniques is also described. In bulk polymerization the catalyst is preferably a halogen substituted acyl peroxide such as trichloroacetyl, trifluoroacetyl, difluoroacetyl, 2,4-dichlorobenzoyl, chloroacetyl, trifluorodichloropropionyl or dichlorofluoroacetyl peroxide, whilst in aqueous suspension a redox system, e.g. a mixture of potassium, sodium, or ammonium persulphate, sodium or potassium bisulphite, and a polyvalent metal salt such as ferrous sulphate or nitrate, may be used.