Due to the rapid development of high frequency and high rate communication technology, polyimide (PI) films with ultra-low dielectric loss (Df) at high frequency, excellent thermal and mechanical properties are urgently needed. A series of PI films with ultra-low Df were prepared by introducing different mesogen units. Among them, one novel PI film with biphenyl liquid-crystal-like units (BAHQ-TFMB) achieve a recorded low Df of 0.00169 (10 GHz) which surpasses previous studies on pure PI bulk films. Importantly, the high degree of collinearity of the friction work (Wf) and Df of PI films (Pearson's r = 0.992) was confirmed, which indicate that Wf among PI macromolecules plays an important role in determining Df of PI films. To reveal underlying reason for reducing the Wf and Df of PI films, the contribution of the degree of orientation and crystallinity of PI films with or without liquid-crystal-like structures were comparative studied. Through a two-dimensional orientation determinant, it is found that increasing the crystallinity of liquid-crystal-like PI films is the main contribution to reducing Wf and corresponding Df of PI films while the orientation of PI films seems to have weak effect. Moreover, BAHQ-TFMB PI film exhibits excellent mechanical properties. The tensile strengths is 145.5 ± 12.0 MPa and Young's moduli is 4.76 ± 0.28 GPa.
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