Facile Strategy for Intrinsic Low‑k Dielectric Polymers: Molecular Design Based on Secondary Relaxation Behavior

An original design strategy for the preparation of polymers with a low dielectric constant is presented. The key to this design strategy is taking the most advantage of the secondary relaxation behavior of the polymer chains to obtain more free volume in the bulk, which can effectively reduce the dielectric constant of the polymer. By using this design strategy, we have successfully synthesized a novel polyimide TmBPHF with a pendant group that consists of a biphenyl unit attached to the meta-position of a phenyl ring that is part of a triaryl unit. The intrinsic k and dielectric loss values of the TmBPHF are 2.09 and 0.0012 at 10 kHz, respectively. More importantly, such outstanding low-k performance remains stable up to 300 °C. The excellent low-k performance of TmBPHF is mainly due to the secondary relaxation, especially the β relaxation, which occurs from the rotation of the pendant group. The TmBPHF film shows an ultralow moisture rate (∼0.17%), which is able to maintain the low-k property stability in different humid environments. Meanwhile, the TmBPHF film also shows excellent thermal stability and excellent mechanical properties, with a glass transition temperature (T g) of 302 °C, 5 wt % decomposition temperature (T d5%) of 549 °C, and residual of 70% at 800 °C under N2. The tensile strength and tensile modulus of the polyimide film are equal to 85.8 MPa and 2.02 GPa, respectively. In addition, the TmBPHF film is soluble in common solvents, which allows simple solution processing and efficient, low-cost, and continuous roll-to-roll processes. The design strategy is beneficial for lowering the k value and simultaneously maintaining the overall properties of polyimides, which possibly could also be extended to other novel high-performance polymer systems.