High-barrier polyimide containing fluorenol moiety: Gas barrier properties and molecular simulations

An intrinsic high-barrier polyimide (9-OH-FPPI) was prepared through the polycondensation reaction of pyromellitic dianhydride (PMDA) with a novel diamine (9-OH-FPDA) containing fluorenol moiety. The synthesized polyimide displays superior barrier performances, possessing water vapor transmission rate (WVTR) and oxygen transmission rate (OTR) low to 1.64 g·m−2·day−1 and 0.66 cm3·m−2·day−1, respectively. Meanwhile, 9-OH-FPPI also demonstrates high thermal stability with a glass transition temperature (Tg) of 410 °C, 5% weight-loss temperature (Td5%) of 577 °C under N2 and coefficient of thermal expansion (CTE) of 5.65 ppm/K. A detailed molecular simulation study as well as positron annihilation lifetime spectroscopy (PALS) and wide angle X-ray diffraction (WAXD) analysis have been carried out to reveal the barrier mechanism. The results reveal that the introduction of fluorenol moiety not only enhances the rigidity and regularity of polymer backbone, but also improves the interchain cohesion of PI matrix, which in turn lead to high crystallinity, low free volume and poor chains mobility of 9-OH-FPPI. The high crystallinity and low free volume decrease the diffusion and solubility of gases in polyimide matrix. In addition, the poor chains mobility further suppresses the gases diffusion. Simultaneous reductions of gases diffusion and solubility promote the barrier properties of 9-OH-FPPI. The as-synthesized polyimide exhibits wide application prospects in the flexible electronic packaging industry. [Display omitted] •A novel diamine containing fluorenol moiety was successfully synthesized.•An intrinsic high-barrier and thermally stable PI was reported.•The barrier properties of PI were improved by the introducing of fluorenol moiety.•The barrier mechanism of PI was revealed by experiments and molecular simulations.•High crystallinity, low free volume and chain mobility led to high gas barrier of PI.