Abstract
AbstractThe polymerization of various monomers in the glassy state was investigated at low temperatures and compared with polymerization in the crystalline state. It was found that acrylonitrile can polymerize in the glassy state in 2‐methyltetrahydrofuran via an anionic mechanism, and the rate of polymerization is much faster in the glassy state than in the crystalline. On the other hand, it was observed that acrylonitrile can be copolymerized with vinyl acetate in glassy mixtures of the two monomers over a wide range of monomer concentrations at low temperatures, below about −160°C. From the monomer reactivity ratio of two monomers in the two component system the polymerization is believed to proceed via a radical mechanism. It was also found that propylene oxide can polymerize only in the glassy state, and the rate of polymerization is quite rapid in matrices of methylene chloride. It was suggested from the effect of various additives on the polymerization that the polymerization proceeds via a cationic mechanism.
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