Vinyl Monomers, Polymers and Supramolecular Assemblies from Aminocaprolactam

α-Aminocaprolactam is a “green” monomer in two ways: it is a fermentation product from sugars, and its derivatives are naturally biocompatible and biodegradable. In this overview, the synthesis of a variety of α-amino-e-caprolactam (ACL) derivatives through reaction with acid chlorides, anhydrides, and alkyl halides is described first. The product vinyl and divinyl derivatives were then polymerized using free radical initiators, and the obtained polymers characterized by solution NMR spectroscopy, differential scanning calorimetry, and thermal gravimetric analysis. The homopolymers of these monomers displayed surprisingly high glass transition temperature (Tg) values plus unexpectedly large sub-Tg transitions that are believed due to relaxation of hydrogen bonding of pendent ACL units that allows group rotation. Finally, bis- and tetra-caprolactams of various diacid chlorides and diisocyantes were synthesized and shown to form self-assembled polymers and networks with excellent physical and thermal properties.