Abstract
A calorimetric technique was used to study the phase state of the “HCN + acetaldehyde” system. Initiation of copolymerization occurs over the whole range of initial concentrations of monomers during defrosting of the system radiolyzed at 77 K in the regions of enhanced molecular mobility (premelting or glass softening). The HCN content in the copolymer monotonously increases with increase in the concentration of this comonomer in the starting mixture. The copolymer contains an insoluble fraction. The system passes completely to a glassy state with ~25% molar HCN. The completely soluble copolymer is formed only if the process is carried out in a system of this kind. The copolymerization in the glassy system occurs by cationic and radical mechanisms. With small doses of preirradiation, the copolymer is formed mainly by the cationic mechanism. With increase of the irradiation dose, the HCN content in the copolymer is increased. The copolymer is much more thermostable than polyacetaldehyde prepared under the same conditions.
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