Abstract
As an example of molecular design of new polymers, structures and properties of poly(ethylene thionoterephthalate) (PET[S(2)]) and the related polymers have been predicted from calculations of ab initio molecular orbital (MO) theory, rotational isomeric state (RIS) scheme, and periodic density functional theory (DFT). The MO calculations were confirmed by NMR experiments and introduced to the RIS scheme for PET[S(2)] to yield its configurational properties, which are compared herein with those of analogous polyester, polythioester, and polydithioester. Configurational properties of randomly thiono-substituted poly(ethylene terephthalate) (PET), PET[S (z) O(1-z) ], were also evaluated as a function of sulfidity (z). On the assumption that the crystal of PET[S(2)] can be expressed as an isomorphic replacement of the PET crystal, the crystal structure was optimized by a periodic DFT simulation and its Young's moduli in the a-, b-, and c-axis directions were, respectively, evaluated to be E(a) = 0.94(7.20) GPa, E (b) = 19.58(22.26) GPa, and E (c) = 142.1(182.4) GPa, where the parenthetic values are those of the PET crystal. There is a possibility that properties of PET[S (z) O(1-z) ] will be controlled between those of PET and PET[S(2)] by adjusting the sulfidity. The potential practical applications of the polythionoesters are also discussed herein. By purely theoretical computations, the structures and properties of the not-yet synthesized polymers were predicted quantitatively; that is, the theoretical molecular design of new polymers has been achieved.