Polymer dielectrics with high dielectric constant are urgently demanded for potential electrical and pulsed power applications. The design of polymers with side chains containing dipolar groups is considered an effective method for preparing materials with a high dielectric constant and low loss. This study synthesizes and comprehensively compare the dielectric properties of novel polyimides with side chains containing urea (BU-PI), carbamate (BC-PI), and sulfonyl (BS-PI) functional groups. The novel polyimides exhibit relatively high dielectric constant and low dielectric loss values due to the enhanced orientational polarization and suppressed dipole-dipole interactions of dipolar groups. In particular, BU-PI containing urea pendant groups presents the highest dielectric constant of 6.14 and reasonably low dielectric loss value of 0.0097. The strong γ transitions with low activation energies derived from dielectric spectroscopy measurements have been further evaluated to demonstrate the enhanced free rotational motion of urea pendant dipoles. In energy storage applications, BU-PI achieves a discharged energy density of 6.92 J cm-3 and a charge-discharge efficiency above 83% at 500 MV m-1. This study demonstrates that urea group, as dipolar pendant group, can provide polymers with better dielectric properties than the most commonly used sulfonyl groups.

Innovative dielectric materials with high-temperature resistance and outstanding dielectric properties have attracted tremendous attention in advanced electronical fields. Polyimide(PI) is considered a promising candidate for the modern electronic industry due to its excellent dielectric properties and comprehensive properties. However, the limited-adjustable range of dielectric constant and the difficulty to obtain a high dielectric constant restrict the application of PI as high dielectric materials. Herein, a novel diamine monomer (2,2\'-bis((methylsulfonyl)methyl)-[1,1\'-biphenyl]-4,4\'-diamine (BSBPA)) containing a rigid biphenyl structure and high dipolar sulfonyl pendant groups is designed for high dielectric polyimides. The rigid biphenyl and polar sulfonyl pendant groups can reasonably optimize the molecular structure and orientational polarization of polyimides to improve their dielectric properties and thermal properties. Moreover, the effect of different bridge linkages on the dielectric properties is studied by using the different dianhydrides. Thus, the PI-BSBPA films especially the DSDA-BSBPA film (DSDA: 3,3\',4,4\'-diphenylsulfonetetracarboxylic dianhydride) achieve great thermal properties (T5%d of 377 °C and Tg of 358 °C) and excellent dielectric properties (6.95 at 1 kHz) along with high discharged energy density of 5.25 J cm-3 and charge-discharge efficiency of 90%. The collaborative control of main-chain and side-chain engineering is effective to endow the polyimides with high-temperature tolerance and high dielectric performance.