ABSTRACT
Cyclopolymerization of 1,5- and 1,6-dienes readily occurs to yield linear, noncrosslinked polymers in contrast to earlier well-accepted theories of crosslinking. The kinetics and mechanism of the radical cyclopolymerization of diallyldimethylammonium chloride has been surveyed. The kinetics of polymerization of aqueous solutions of diallyldimethylammonium chloride in inverse emulsion was studied and the mechanism discussed. Radical polymerization of acrylic propionic anhydride as a monoene counterpart of acrylic anhydride was investigated in order to obtain supporting evidence for a proposed mechanism based on polymerization equilibrium for the cyclopolymerization of acrylic anhydride. Poly(divinylformal), prepared by photoinitiated polymerization, also gave an x-ray pattern showing partial crystallinity. On the basis of the present evidence it appears that, in one case of cyclopolymerization or another, all of the factors considered such as statistical probability, thermodynamic stability, entropy effects, non-conjugated interactions, and polymerization conditions are important in understanding the mechanism of cyclopolymerization.
