Impact of the Pendant Group on the Chain Conformation and Bulk Properties of Norbornene Imide-Based Polymers.

Three series of well-defined norbornene imide-based polymers with different pendant groups were synthesized to investigate the effect of the pendant group on the polymer conformation in solution and bulk melt properties. Each of these three series was examined by analyzing the polymers' bulk z-average radius of gyration via static light scattering and the polymers' melt viscoelastic properties via oscillatory measurements and differential scanning calorimetry. Sterically bulky pendant wedge groups modestly increase the rodlike conformation of the norbornene-imide polymer, however, the inherent rigidity of the polymer main-chain can still be observed with less bulky substituents. In stark contrast, the different side groups significantly impacted the bulk viscoelastic and thermal properties. By increasing the pendant group size, the chain diameter of the polymer increases and lowers the entanglement modulus. Finally, as the wedge pendant group size increases, the segmental relaxation time and the fragility index of these norbornene-based polymers are decreased.