Impact of Backbone Amide Substitution at the Meta- and Para-Positions on the Gas Barrier Properties of Polyimide

This study designed and synthesised a meta-amide-substituted dianiline monomer (m-DABA) as a stereoisomer of DABA, a previously investigated para-amide-substituted dianiline monomer. This new monomer was polymerised with pyromellitic dianhydride (PMDA) to prepare a polyimide film (m-DABPI) in a process similar to that employed in a previous study. The relationship between the substitution positions on the monomer and the gas barrier properties of the polyimide film was investigated via molecular simulation, wide-angle X-ray diffraction (WXRD), and positron annihilation lifetime spectroscopy (PALS) to gain deeper insights into the gas barrier mechanism. The results showed that compared with the para-substituted DABPI, the m-DABPI exhibited better gas barrier properties, with a water vapour transmission rate (WVTR) and an oxygen transmission rate (OTR) as low as 2.8 g·m(−2)·d(−1) and 3.3 cm(3)·m(−2)·d(−1), respectively. This was because the meta-linked polyimide molecular chains were more tightly packed, leading to a smaller free volume and lower molecular chain mobility. These properties are not conducive to the permeation of small molecules into the film; thus, the gas barrier properties were improved. The findings have significant implications for the structural design of high-barrier materials and could promote the development of flexible display technology.