Comparison of Homo-Polyimide Films Derived from Two Isomeric Bis-Benzimidazole Diamines.
Comparison of Homo-Polyimide Films Derived from Two Isomeric Bis-Benzimidazole Diamines.
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DOI：
10.3390/molecules28134889
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发表时间：
2023-06-21
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含苯并咪唑的杂芳族聚酰亚胺（PI）由于其对PI性能的积极影响而引起了极大的关注。本文报道了含4，4 ′-[5，5 ′-联-1H-苯并咪唑]-2，2 ′-二基双苯胺（4-AB）的PI的研究。然而，含有4-AB异构体之一的3，3 ′-[5，5 ′-联-1H-苯并咪唑]-2，2 ′-二基双苯胺（3-AB）的均聚聚酰亚胺（homo-PI）的报道较少。本文研究了氨基位置对均聚PI性能的影响。结果表明，4-AB中胺基N的净电荷比3-AB低，导致4-AB的反应活性更高。因此，含有4-AB的PI显示出更好的机械性能。分子模拟证实，3-AB及其相应的PI链表现出扭曲的构象，导致含有3-AB的PI膜具有较浅的颜色。此外，计算出3-AB结构与4-AB相比具有更高的旋转能，导致由3-AB制备的PI的玻璃化转变温度（Tg）更高。另一方面，与由3-AB制备的PI相比，含有4-AB的PI表现出更高水平的分子线性，导致更低的热膨胀系数（CTE）。此外，所有PI均显示出较高的热稳定性，5%重量损失温度高于530 °C，Tg高于400 °C。
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 of 4-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 in 4-AB was lower than that of 3-AB, resulting in higher reactivity of 4-AB. Consequently, PIs containing 4-AB displayed better mechanical performance. Molecular simulation confirmed that 3-AB and its corresponding PI chain exhibited distorted conformation, leading to the PI films containing 3-AB having a lighter color. In addition, the 3-AB structure was calculated to have higher rotational energy compared to 4-AB, resulting in a higher glass transition temperature (Tg) in PIs prepared from 3-AB. On the other hand, PIs containing 4-AB exhibited a higher level of molecular linearity, leading to a lower coefficient of thermal expansion (CTE) compared to PIs prepared from 3-AB. Furthermore, all PIs showed higher thermal stability with a 5% weight loss temperature above 530 °C and Tg higher than 400 °C.
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