Design and synthesis of high heat-resistant, soluble, and hydrophobic fluorinated polyimides containing pyridine and trifluoromethylthiophenyl units

Abstract

In this study, a novel diamine monomer, 4-(4-trifluoromethylthiophenyl)-2,6-bis(4-aminophenyl)pyridine (FTPAP) was synthesized through two-step reaction from 4-trifluoromethylthiobenzaldehyde and 4-nitroacetophenone as raw materials, and then the structure of FTPAP was characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance, and mass spectrometry. A series of fluorinated polyimides were prepared from FTPAP with five commercial dianhydrides, namely, pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphtahalic anhydride, benzophenone tetracarboxylic dianhydride, and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride. The structure and performance of the fluorinated polymers were fully characterized by FTIR, differential scanning calorimetry, thermogravimetric analysis, and wide-angle X-ray diffraction (WAXD). The inherent viscosity of polymers ranged from 0.41 to 1.45 dL g−1. These polymers displayed good solubility in polar aprotic solvents, such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone, at room temperature or on heating. Furthermore, they exhibited outstanding thermal stability with glass transition temperatures beyond 305°C, and the temperature of 10% weight loss was in the range of 514–573°C with more than 56% residue at 800°C under nitrogen. Moreover, they showed high optical transparency with the cutoff wavelengths in the range of 385–457 nm and excellent hydrophobic property with contact angle in the range of 82.8–97.6°. In addition, the results of WAXD indicated that all of the polymers presented amorphous structure.