Computational Characterization of Nylon 4, a Biobased and Biodegradable Polyamide Superior to Nylon 6

[Image: see text] This study is an attempt to develop a theoretical methodology to elucidate or predict the structural characteristics and the physical properties of an isolated polymeric chain and its crystalline state precisely and quantitatively. To be more specific, conformational characteristics of a biobased and biodegradable polyamide, nylon 4, in the free state have been revealed by not only ab initio molecular orbital calculations on its model compound but also nuclear magnetic resonance experiments for the model and nylon 4. Furthermore, the crystal structure and solid-state properties of nylon 4 have been elucidated by density functional theory calculations with a dispersion force correction under periodic boundary conditions. In the free state, the nylon 4 chain forms intramolecular N–H···O=C hydrogen bonds, which force the polymeric chain into distorted conformations including a number of gauche bonds, whereas nylon 4 crystallizes in the fully extended all-trans structure (α form) that is stabilized by intermolecular N–H···O=C hydrogen bonds. The intermolecular interaction energy (ΔE(CP)) in the crystal was accurately calculated via a counterpoise (CP) method contrived here to correct the basis set superposition error, and the ultimate crystalline modulus (E(b)) in the chain axis (b axis) direction at 0 K was also evaluated theoretically. The results were compared with those obtained from the α and γ crystalline forms of nylon 6, and, consequently, the superiority of nylon 4 to nylon 6 in thermal stability and mechanical properties was indicated: the ΔE(CP) and E(b) values are, respectively, −214 cal g(–1) and 334 GPa (nylon 4), −191 cal g(–1) and 316 GPa (α form of nylon 6), and −184 cal g(–1) and 120 GPa (γ form of nylon 6). In conclusion, nylon 4 is expected to be put to practical use as a tough environmentally friendly polyamide.