Reduced Coefficients of Linear Thermal Expansion of Colorless and Transparent Semi-Alicyclic Polyimide Films via Incorporation of Rigid-Rod Amide Moiety: Preparation and Properties.

Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3',4,4'-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4'-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4'-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including -methyl-2-pyrrolidone (NMP) and ,-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-I (HPMDA-MeDABA) and PI-II (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-I and PI-II). PI-I and PI-II showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 μm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10/K for PI-I and 27.7 × 10/K for PI-I in the temperature range of 50-250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures () higher than 430 °C and glass transition temperatures () in the range of 349-351 °C.