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

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 -butylchlorodiphenylsilane (TBDPSCl), and their structures were confirmed by H NMR and IR spectra. The bulky nonpolar -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 ( ) 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, CHCl, acetone, and toluene) is significantly improved. Furthermore, Si-PI films still maintain relatively good thermal properties with the 5% weight loss temperature ( ) in the range 470-491 °C under a nitrogen atmosphere and the glass transition temperature ( ) in the range 245-308 °C.