**Abstract**

Fluorinated polyimides were prepared from the twisted benzidine monomer containing two trifluoromethyl (CF3) groups on one aromatic ring. The diamine monomer having a rigid and nonplanar structure was polymerized with typical dianhydride monomers including BPDA, BTDA, ODPA, 6-FDA, and PMDA, to obtain the corresponding polyimides. Most polyimides are soluble in organic solvents due to their twisted chain structure and can be solution cast into flexible and tough films. These films have a UV-vis absorption cut-off wavelength at 354– 398 nm and a light transparency of 34–90% at a wavelength of 550 nm. They also have tensile strengths of 92–145 MPa and coefficients of thermal expansion (CTE) of 6.8–63.1 ppm/°C. The polymers exhibited high thermal stability with 5% weight loss at temperatures ranging from 535 to 605°C in nitrogen and from 523 to 594°C in air, and high glass temperature (*T*g) values in the range of 345–366°C. Interestingly, some of the soluble polyimides showed thermo-responsive behaviors in organic solvents presumably due to the multiple hydrogen bondings with unsymmetrically positioned two CF3 groups along the polymer chains.

**Keywords:** fluorinated polyimides, rigid and nonplanar structure, flexible and tough films, thermal stability, high glass temperature, coefficients of thermal expansion
