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. Two especially attractive uses for photopolymerizable oxetanes are 3D imaging applications (sometimes termed "additive manufacturing") and dental composites. The use of this technology can also be applied to many other photocurable applications including: sealants, encapsulants, conformal coatings, decorative and protective coatings for metals, glass, wood and plastics. UV curable oxetane-functional silicones are excellent prospective materials for release coatings. Essentially, this novel UV and visible light curable oxetane materials can be applied to any application where currently epoxide monomers and epoxide functional oligomers are used.