Comparison of Homo-Polyimide Films Derived from Two Isomeric Bis-Benzimidazole Diamines

Heteroaromatic polyimides (PIs) containing benzimidazole have attracted tremendous attention due to their positive impact on the properties of PIs. Some research on PIs containing 4,4′-[5,5′-bi-1H-benzimidazole]-2,2′-diylbis-benzenamine (4-AB) has been reported. However, reports are lacking on homo-polyimides (homo-PIs) containing 3,3′-[5,5′-bi-1H-benzimidazole]-2,2′-diylbis-benzenamine (3-AB), which is one of the isomers of4-AB. In this paper, the influence of amino groups’ positions on the performance of homo-PIs was investigated. It was found that the net charge of the amine N group in4-ABwas lower than that of3-AB, resulting in higher reactivity of4-AB. Consequently, PIs containing4-ABdisplayed better mechanical performance. Molecular simulation confirmed that3-ABand its corresponding PI chain exhibited distorted conformation, leading to the PI films containing3-ABhaving a lighter color. In addition, the3-ABstructure was calculated to have higher rotational energy compared to4-AB, resulting in a higher glass transition temperature (Tg) in PIs prepared from3-AB. On the other hand, PIs containing4-ABexhibited a higher level of molecular linearity, leading to a lower coefficient of thermal expansion (CTE) compared to PIs prepared from3-AB. Furthermore, all PIs showed higher thermal stability with a 5% weight loss temperature above 530 °C andTghigher than 400 °C.Keywords:heteroaromatic polyimides;isomeric diamine;bis-benzimidazole