Ultralow Coefficient of Thermal Expansion and a High Colorless Transparent Polyimide Film Realized Through a Reinforced Hydrogen-Bond Network by In Situ Polymerization of Aromatic Polyamide in Colorless Polyimide

Colorless polyimides (CPIs) are a key substrate material for flexible organic light-emitting diode (OLED) displays and have attracted worldwide attention. Here, in this paper, the dispersion and interfacial interaction of aromatic polyamide (PA) in CPI (synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2′-bis(trifluoromethyl)benzidine (TFMB)) were significantly improved by in situ polymerization, and colorless transparent macromolecular polyimide composites (CPI-PAx) were successfully prepared by PA and CPI. By adjusting the ratio of PA to CPI, a high-performance engineering plastic with excellent film-forming properties was obtained. Molecular simulations confirmed the uniform distribution of PA in CPI and its interaction in polymers. In CPI-PAx, the CPI was locked by the PA chain, and numerous molecular chains were mutually entangled to form a hydrogen-bond network structure. Due to the strong interaction between the chains imparted by the hydrogen bonds of the PA, they do not slide under external forces and heating. In addition, the additive PA has excellent dimensional stability, thermal, and mechanical properties, and CPI has outstanding optical properties, so the synthesized CPI-PAx combines the comprehensive properties of PA and CPI. The CPI-PAx has excellent thermal and mechanical properties, with a thermal decomposition temperature of 499 °C, a glass transition temperature of 385 °C, a coefficient of thermal expansion of 0.8 ppm K–1, a tensile strength of 50.9 MPa, and an elastic modulus of 3.9 GPa. Particularly, CPI-PAx has a 90% transmittance in the visible region. These data prove that the strategy of combining PA and CPI by in situ polymerization is an effective method to circumvent the bottleneck of CPI in the current flexible window application, and this design strategy is universal.