Simultaneously Improving the Optical, Dielectric, and Solubility Properties of Fluorene-Based Polyimide with Silyl Ether Side Groups

[Image: see text] Three fluorene-based polyimides with silyl ether groups (Si–PIs) were successfully synthesized by a simple and efficient silicon etherification reaction of hydroxyl-containing polyimides (OH–PIs) and tert-butylchlorodiphenylsilane (TBDPSCl), and their structures were confirmed by (1)H NMR and IR spectra. The bulky nonpolar tert-butyldiphenylsilyl (TBDPS) side groups in the modified PI unit instead of the strong electron donor −OH group is conducive to decreasing electronic conjugation and charge transfer (CT) interaction along the PI chain. Accordingly, the optical, dielectric, and solubility properties of the modified Si–PI films are simultaneously improved compared with the precursor OH–PI films. The modified Si–PI films demonstrate a meaningful enhancement in the transmittances at a wavelength of 400 nm (T(400)) to 74–81% from 42 to 55% of OH–PI films and the regeneration of fluorescence characteristics. The dielectric constant and loss of Si–PI films are also obviously reduced to 2.63–2.75 and 0.0024–0.0091 at 1 kHz from 4.19 to 4.78 and 0.0173–0.0295 of OH–PI films, respectively, due to substituted with the bulky nonpolar TBDPS groups to increase the free volume and hydrophobicity of Si–PI films. The solubility of Si–PIs in low- or nonpolar solvents (such as CHCl(3), CH(2)Cl(2), acetone, and toluene) is significantly improved. Furthermore, Si–PI films still maintain relatively good thermal properties with the 5% weight loss temperature (T(5%)) in the range 470–491 °C under a nitrogen atmosphere and the glass transition temperature (T(g)) in the range 245–308 °C.