With the rapid development of photoelectric devices, the demand for black polyimide (BPI) with excellent masking ability is growing, but existing BPI doped with black substrates has serious insulation and mechanical performance deficiencies. To solve the problem, the intrinsic BPI with excellent comprehensive performance is highly desirable. In this work, tetraphenylcyclopentadienone (TPCP) was chosen as a chromophore, a novel diamine (TPCPtPPDA) containing TPCP grafted with biphenyl groups was synthesized, and TPCPtPPDA was then polymerized with 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) to obtain a black polyimide (TPCPtPPPI). The TPCPtPPPI showed full absorption of visible light with cutoff wavelength (λ_cut) high to 713 nm and Commission International Eclairage (CIE) lab color parameter L* of 0.82. By calculating the frontier molecular orbitals and the nature of electron transitions, the excellent light absorption property was attributed to the electron transition from HOMO to LUMO occurring in the diamine moieties, with the charge transfer mainly from the terphenyl moieties in 2 and 5 positions to the central cyclopentadienone core. Meanwhile, TPCPtPPPI also had excellent thermal, electrical and mechanical performances and solubility by introduction of rigid non-planar propeller-shaped structure. This work provides a promising strategy for constructing high-performance soluble intrinsic BPI and related polymers with full absorption of visible light.

随着光电器件的快速发展，对具有优异掩蔽能力的黑色聚酰亚胺（BPI）的需求越来越大，但现有掺杂黑色基板的BPI存在严重的绝缘和机械性能缺陷。为了解决这个问题，非常需要具有优异综合性能的内在BPI。在这项工作中，选择四苯基环戊二烯酮（TPCP）作为发色团，合成了一种含有TPCP接枝联苯基的新型二胺（TPCPtPPDA），然后TPCPtPPDA与4,4'-（六氟异亚丙基）二邻苯二甲酸酐（6FDA）聚合得到黑色聚酰亚胺 (TPCPtPPPI)。TPCPtPPPI 在截止波长 ( λ _cut) 高达 713 nm，国际照明委员会 (CIE) 实验室颜色参数L*为 0.82。通过计算前沿分子轨道和电子跃迁的性质，优异的光吸收性能归因于二胺部分发生从 HOMO 到 LUMO 的电子跃迁，电荷主要从 2 位和 5 位的三联苯部分转移到中央环戊二烯酮核心。同时，TPCPtPPPI还通过引入刚性非平面螺旋桨状结构，具有优异的热、电、机械性能和溶解性。这项工作为构建高性能可溶性本征 BPI 和相关聚合物提供了一种有前途的策略，可以完全吸收可见光。