High performance imide oligomers and thermosets derived from 9,9-bis (3,4-dicarboxyphenyl)fluorene dianhydride

Abstract

In this work, a new class of imide oligomers and thermosets with improved overall properties was developed by exploiting the steric effects of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF). First, a model compound was prepared from BPAF and aniline. This model compound possessed a twisted architecture, with two dihedral angles between fluorene ring and phthalimide segments of around 75°. Then, an array of phenylethynyl-endcapped imide oligomers was synthesized from BPAF, 4-phenylethynyl phthalic anhydride (4-PEPA), and aromatic diamines (4,4′-oxydianiline (4,4′-ODA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), m-phenylenediamine (m-PDA)). The BPAF-derived imide oligomers exhibited improved organic solvents solubility and higher melt viscosity compared to those based on 2,3,3′,4′-biphenyltetracarboxylic dianhydride (3,4′-BPDA), due to their bulky, twisted, and sterically hindered cardo architectures. The imide oligomers under pressure were converted into thermosets by the thermal crosslinking of phenylethynyl at 370 °C for 2 h. The BPAF-derived thermosets exhibited much higher glass transition temperature (Tg) (＞ 404 °C), 5% weight-loss temperature (T5%) (＞ 549 °C) in an air environment, and more excellent high-frequency dielectric properties from 30 to 45 GHz (dielectric constant as low as 2.85 and dielectric loss factor as low as 0.0037) while possessing comparable or even better mechanical properties relative to the 3,4′-BPDA-derived polymers. Therefore, these polymers based on BPAF may have potential applications as matrix resins for heat-resistant, structural and functional composites.