Using Dicyclopentadiene-Derived Polyarylates as Epoxy Curing Agents To Achieve High Tg and Low Dielectric Epoxy Thermosets

To achieve high- T g and low-dielectric epoxy thermosets, four dicyclopentadiene-derived polyarylates (26-P, 26-M, 236-P, and 236-M) were prepared from 2,6-dimethyl (or 2,3,6-trimethyl) phenol-dicyclopentadiene adduct with terephthaloyl (or isophthaloyl) chloride by high-temperature solution polymerization. The resulting polyarylates, exhibiting active ester linkages (Ph-O-(C=O)-) are found to be reactive toward a commercial dicyclopentadiene phenol epoxy (HP7200) in the presence of some lone-pair electron-containing compounds. Five compounds including 4-dimethylaminopyridine (DMAP), imidazole, 2-methylimidazole, triphenylphosphine, and triphenylimidazole have been evaluated as a catalyst for the curing reactions. We found that DMAP, with the smallest p K b among them, is the best catalyst according to differential scanning calorimetry, infrared, and thermal analyses. The thermal and dielectric properties of the polyarylate/HP7200 thermosets are evaluated. We found that they exhibit a high T g characteristic (e.g., T g is 238 °C for DMAP-catalyzed, 236-P/HP7200 thermoset). Furthermore, because of the hydrophobic methyl and cycloaliphatic moieties, and the secondary hydroxyl-free structure, polyarylate/HP7200 thermosets show a relative low-dielectric constant of around 2.75 U. The detailed structure-properties relationship is discussed in this work.