Low-κ, low CTE, high-temperature epoxy resin with high storage modulus based on spirobisindane for high-frequency electronic circuit field

Abstract

High-temperature thermosetting resin with low dielectric constant (κ), low thermal expansion coefficient (CTE), and high modulus are drawing more and more attention from scientists and engineers in the field of the high-frequency circuit, 5G and 6G communication networks to improve the signal transmission speed. Epoxy resin, as one of the important thermosetting resin members, possesses excellent properties such as heat resistance, cohesiveness, and reactivity. However, Epoxy resin was usually mixed with different inorganic fillers to meet the above requirements, especially to decrease the κ and CTE. In this work, a new class of spirobisindane epoxy resin monomer (TSDEP) was synthesized by a classic two-step method based on 3,3,3′,3′-tetramethyl-1,1′-spirobisindane-6,6′-diol (TSD). Due to the highly distorted rigid structure of TSD, the movement of the TSDEP molecular segment is subject to more restrictions after being cured, and the free volume will increase. After cured by 4,4′-diamino diphenyl sulfone (DDS), the TSDEP/DDS resin exhibited many desirable physical properties, e.g., low dielectric constant (∼3.45, 1 MHz), low dielectric loss (∼0.025, 1 MHz), low coefficient of thermal expansion (CTE, 72 ppm/ °C, 35–150 °C), high glass transition temperature (Tg > 241 °C) and high thermal stability (Td5%∼400 °C). Furthermore, TSDEP/DDS exhibited excellent mechanical rigidity with a storage modulus of ∼ 3.1 GPa. Compared with TSDEP/DDS, 4-methylhexahydrophthalic anhydride (MHHPA) cured TSDEP system showed lower κ (∼3.09) and dielectric loss (0.015) due to weaker polar ester groups instead of more polar hydroxy groups.