POLYMERIZATION UNDER A PRESSURE OF 6-GPA

Pressures of 6 GPa (ref 52) generated in a tetrahedral anvil pressure apparatus were used for polymerization of addition monomers. With this technique, polymers of moderate and high molecular weight were obtained from selected α-olefins, internal olefins, dienes, and trioxane. The polymers were characterized by their elemental analysis and IR and 1H NMR spectra and have the structure of addition polymers without rearrangements. Success of the polymerization depended on the proper containment of the monomers, which were usually low-boiling liquids; the reaction vessels, specially designed for these pressure experiments, were sealed platinum ampules. The polymerization of a number of monomers which had not been polymerized before has been achieved. It depended on the favorable dependence of the rate of propagation over the rate of termination or transfer. The polymerization reaction mechanism appears to be a thermally initiated radical process with the possible exception of trioxane. © 1979, American Chemical Society. All rights reserved.