2‐Oxazolines (2‐OZO) are 5‐membered cyclic imino ethers whose cationic ring‐opening polymerization (CROP) mechanism and resulting polymer properties are extensively studied. However, also 6‐ and 7‐membered cyclic imino ethers can be polymerized via CROP. Together with the much less studied 4‐ and 5‐substituted main‐chain chiral poly(2‐oxazoline)s (P‐2‐OZO), these compounds are interesting monomers to enhance the versatility of (co)poly(cyclic imino ether)s. To emphasize the potential of such alternative cyclic imino ether monomers, we provide an overview on the polymerizations of 2‐oxazine (2‐OZI) and chiral 4‐ and 5‐substituted 2‐OZO as well as of selected properties of the resulting polymers. In addition, the hydrolysis of these polymers into the corresponding poly(alkylene imine)s will be addressed.
