| 摘要 |
In the copolymerization under reflux in a solvent in which the copolymer is insoluble, e.g. water and in the presence of a catalyst of a mixture of compounds containing the group CH2=C< having different vapour pressures and different rates of acceptance into the copolymer molecules, the monomer of greater vapour pressure having at the boiling point of the solution a vapour pressure and solubility such that a detectable change in temperature results when 0.005 to 0.1 mols. per litre of solution are vaporized, a mixture of the monomers in a predetermined ratio is continuously added at such a rate as to maintain the boiling temperature and rate of reflux constant. Suitable monomeric mixtures are acrylonitrile with methyl acrylate or methacrylate, styrene, vinyl acetate, vinyl pyridines, acrylamide, substituted acrylamides or N-vinyl carbazole; vinyl acetate and 2-vinyl pyridine; methyl methacrylate and styrene; methyl acrylate and acrylamide, the first-named being the "control" monomer. Methacrylonitrile may also be used as the "control". Suitable catalysts are potassium and ammonium persulphates and sodium perborate with sodium bisulphite as activator. The initial monomers are added to the water in a ratio yielding a copolymer of the desired composition and equilibrium of the refluxing reaction mixture is maintained by adding the monomers in a ratio equivalent to that of the first copolymer formed or that accepted by the copolymer. Copolymer may be continuously withdrawn and any water or catalyst removed therewith may be made up. Polymerization is terminated by adding an inhibitor, such as hydroquinone, by filtering-off the product and rapidly washing or by pouring the reaction mixture into a large volume of water. The products are of uniform composition and molecular weight. Examples describe the preparation of copolymers containing (1) 90 per cent acrylonitrile and 10 per cent vinyl acetate; (2) 90 per cent acrylonitrile and 10 per cent styrene; (3) 85 per cent acrylonitrile and 15 per cent acrylamide; (4) 80 per cent acrylonitrile and 20 per cent N-vinyl carbazole. The products of examples (2) and (3) formed clear solutions in dimethyl formamide from which fibres were spun into a setting bath of isopropanol and stretched. After washing and drying the fibres were re-stretched in heated air. Specifications 593,292 and 682,181 are referred to.
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