Verfahren zur Herstellung von polymeren stickstoffhaltigen Produkten

摘要

763,635. Cellulose derivatives; artificial filaments &c. ROHM & HAAS CO. March 29, 1954 [April 10, 1953], No. 9093/54. Classes 2 (2) and 2 (6). [Also in Groups IV (b), IV (c), V, VI and VIII] Vinyl ethers of the formula and ureido derivatives thereof obtained by subsequent reaction with ammonia or amines, wherein Z is a methylene or polymethylene group optionally carrying hydrocarbon substituents and containing not more than seven carbon atoms, and R1 and R11 are alkyl groups when Z is such that O and N are separated by not more than 3 carbon atoms, and are hydrogen or alkyl groups when Z is such that O and N are separated by more than 3 carbon atoms, alone or admixed with one or more other monomers, are polymerized in bulk, aqueous emulsion or organic solution in the presence of a polymerization catalyst. Alternatively, the monomers may be reacted with natural or pre-formed synthetic polymers, e.g. cellulose, rayon, cotton, silk, wool, blood, polyamine resins, acrylic resins, alkyd resins and polyvinyl alcohol resins. Reaction products with blood may be further polymerized. The monomers may also be mixed with alkyd resins and a polyfunctional acid such as adipic acid and polymerized in presence of an acid catalyst. The other co-monomers may be acrylates (e.g. methyl, ethyl, propyl and butyl acrylates), methacrylates (e.g. methyl, ethyl, isopropyl, butyl, tert.-butyl, and tert.-amyl methacrylates), acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, styrene, vinyl esters or mixtures thereof. In aqueous emulsion the emulsifier may be sodium octylphenoxyethoxyethoxyethyl sulphonate. Specified solvents are dimethylformamide and toluene. Exemplified vinyl ethers are 2-vinyloxy-4- methyl - 4 - pentylisocyanate, 2 - isocyanatoisobutyl vinyl ether and 2-ureidoisobutyl vinyl ether. The catalyst may be azodiisobutyronitrile; azodiisobutyramide; dimethyl, diethyl or dibutyl azodiisobutyrate; azobis- (α : γ - dimethylvaleronitrile); azobis - (α- methylbutyronitrile; azobis - (α - methylvaleronitrile) ; dimethyl or diethyl azobismethylvalerate; benzoyl, methylethylketone or caproyl peroxide; tert.-butyl hydroperoxide; butyl perbenzoate; or in aqueous systems ammonium, sodium or potassium persulphate in conjunction with sodium hydrosulphite. The above polymers may be after-treated with amines to yield polyureido derivatives. Thus, (1) a toluene solution of polymerized 2-isocyanatoisobutyl vinyl ether yields a gel on treatment with iminobispropylamine; (2) an acetone solution of polymerized 2-isocyanatoisobutyl vinyl ether yields a dimethylaminopropylurea derivative on treatment with dimethylaminopropylamine; and (3) a toluene solution of a 2-isocyanatoisobutyl vinyl ether/ methyl methacrylate copolymer increases in viscosity on treatment with iminobispropylamine. The above polymers, in particular polymerized 2-isocyanatoisobutyl vinyl ether, may be added to cellulose acetate dopes. Films or fibres formed from thus treated dopes possess improved tensile strength and are highly resistant to solvents' after heat treatment.