Abstract
Heteroaromatic polymers are considered to be high performance organic materials due to their unique and highly attractive properties, including outstanding thermal and mechanical resistance, that arise from their aromatic structure and strong interactions between macromolecular chains. Modification or designing new molecular architectures with tailored physico-chemical characteristics allows expanding the applications of these materials in various advanced technologies. Herein, a series of polymers containing bulky phenoxyphthalonitrile pendant units was synthesized and their physical properties were studied and correlated with their conformational parameters, as well as free and van der Waals volumes. For comparison, the related polymers without lateral moieties were also investigated to highlight the effect of bulky substituent on the polymer rigidity. Thus, it is shown that conformational rigidity determines the packing of macromolecules in solid state, and, therefore, the free volume, glass transition, and decomposition temperatures. The values found experimentally for T (g) correlate well with those obtained using the conformational rigidity parameters. The dependence of T (g) of these polymers on Kuhn segment is described by linear equations, with very good factors of convergence. The correlations established by Monte Carlo method allow obtaining the T (g) values for related polymers where the experimental measurement of this parameter is difficult.