New processes are proposed for preparation of novel, highly reactive, renewable substrate oxetane polymers, making it possible to use cationic oxetane photopolymerizations in many high-speed coatings, printing inks, adhesives, as well as in additive manufacturing processes such as stereolithography, digital imaging and in ink-jet printing. Specifically, an epoxide accelerant, such as 2,2-substituted epoxide, 2,2,3-substituted epoxide, 2,2,3,3-substituted epoxide, and mixtures thereof, is reacted with one or more equivalents of a 3-monosubstituted oxetane or a 3,3-disubstituted oxetane.