Design and Synthesis of Fluorinated Polyimides with Low Thermal Expansion and Enhanced Dielectric Properties

Modern microelectronics industries urgently require dielectric materials with low thermal expansion coefficients, low dielectric constants, and minimal dielectric loss. However, the design principles of materials with low dielectric constants and low thermal expansion are contradictory. In this study, a new diamine monomer containing a dibenzocyclooctadiene unit (DBCOD-NH2) was designed and synthesized, which was subsequently polymerized with high fluorine content 4,4′-hexafluoroisopr-opylidene diphthalic anhydride and 4,4′-diamino-2,2′-bis(trifleoromethyl)biphenyl to obtain a series of fluorinated polyimides (PIs). Due to the unique conformational transition of the eight-membered carbon ring, the resulting PI can reach a low averaging thermal expansion coefficient (CTE) of only 12.27 ppm/K over 5–150 ℃ with a size change rate of only 0.16 %. Surprisingly, the synergistic effect of DBCOD-NH2 with the other two monomers enhances the dielectric performance of the PIs. At an electric field frequency of 10 MHz, the dielectric constant (Dk) and the dielectric loss (Df) can be reduced to as low as 2.61 and 0.00194, respectively. The strategy used herein largely tackles the challenge of balancing low Dk with low CTE. Furthermore, these PI films also exhibit good thermal stability (with 5 wt% weight loss temperatures ranging from 453 to 537 ℃ in N2, and glass transition temperatures of 305–337 ℃) and robust mechanical properties (with a tensile modulus of 1.88–2.29 GPa and an elongation at break of 6.36–8.11 %). The combination of low thermal expansion and excellent dielectric properties renders these PIs highly promising for applications in the microelectronics and telecommunications industries.