Abstract
Abstract The influence of acetic anhydride on the polymerization of formaldehyde, which was carried out by means of initiation with an acidic catalyst in liquid carbon dioxode, was studied at 20 to 40°C. Acetic anhydride decreased the polymer yield and the degree of polymerization of the polymer resulting from the polymerization with acetic acid. Moreover, the over-all rate of polymerization with acetic acid in the presence of acetic anhydride deviated from a first-order equation with respect to the monomer concentration. On the other hand, the polymerization which was initiated by dichloroacetic acid was not affected by the presence of acetic anhydride. On the basis of a kinetical consideration, it can be said that the termination which was proportional to the square of the concentration of the initiating species was caused by the presence of acetic anhydride in the polymerization with acetic acid. The rate constants and the activation energies of the elementary processes were estimated, and a rate equation satisfying the experimental results was presented.
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