Two diaminocalix[4]
arene monomers were synthesized from p-tertbutylcalix[4]arene through a 4-step reaction sequence. New copoly(amic acid)s containing calix[4]arene moieties on the polymer backbone were successfully synthesized in N-methyl-2-pyrrolidone by polycondensations of 4,4ะ-oxydiphthalic anhydride (ODPA) with the diaminocalix[4]arene monomers using 4,4ะ-oxydiphenylene diamine (ODA) as a comonomer. These copoly(amic acid)s were soluble in aprotic polar solvents, so that they can be processed in various ways. The copoly(amic acid) precursors were thermally converted to the corresponding copolyimides in films. The copolyimide films are amorphous, but insoluble in common solvents. They are thermally stable up to 366ยฐC. The copolyimides exhibit relatively high TEC's, low T g 's, low refractive index, low dielectric constant, low optical anisotropy, low dielectric anisotropy, and low water uptake, compared to those of conventional ODPA-ODA polyimide. These property characteristics were interpreted in regard to bulky, cone-like calix[4]arene moieties and their effects on the chain conformation and morphological structure. The processability and property characteristics support that both of the copolyimides containing calix[4]arene moieties are potential candidate materials suitable for membranes, antioxidant additives, chemical sensor devices, and microelectronic devices.