A new aromatic diacid monomer, N, N-bis(4-carboxyphenyl)-4-trifluoromethylaniline, was synthesized by the substitution reaction of 4-trifluoromethylaniline with 4-fluorobenzonitrile, followed by alkaline hydrolysis of the dinitrile intermediate. Several polyamides with 4-trifluoromethyltriphenylamine moieties were prepared from the diacid and various aromatic diamines via the direct phosphorylation polycondensation. All the polyamides were amorphous and readily soluble in many polar organic solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and could be solution-cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability with glass transition temperatures of 260–330°C, 10% weight-loss temperatures above 500°C, and char yields higher than 60% at 800°C in nitrogen. These polymers had low dielectric constants of 3.35–3.72 (100 Hz), low water uptake of 1.80–2.60%, and high transparency with an ultraviolet–visible absorption cutoff wavelength in the range of 378–390 nm. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide–coated glass substrate exhibited a reversible oxidation redox coupled with oxidation half-wave potentials ( E 1/2) of 0.95–1.04 V versus silver/silver chloride in an acetonitrile solution.
A series of new polyarylates bearing cardo xanthene groups were synthesized by phase-transfer-catalyzed interfacial polycondensation of 9,9-bis[4-(4-chloroformylphenoxy)phenyl]xanthene with various bisphenols containing the isopropylidene, hexafluoroisopropylidene, 1-phenylethylidene, diphenylmethane, cyclohexane, and xanthene structures. High-molecular-weight polyarylates with number-average molecular weight and polydispersity index in the range of 30,100–35,300 and 1.82–2.17, respectively, exhibited high glass transition temperatures ranged from 226°C to 261°C, and their 10% weight loss temperatures were in the range of 421–452°C with char yields above 45% at 700°C in nitrogen. All the polyarylates were amorphous and readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidinone at room temperature and could be cast into tough, transparent, and flexible films with tensile strengths of 85.6–108.3 MPa, elongations at break of 2–3%, and tensile moduli of 7–9 GPa.
A series of new fluorinated copoly(pyridine ether imide)s were prepared by thermal imidization of polyamide acid derived from 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (BATB), 4-(4-trifluoromethylphenyl)-2,6-bis(4-aminophenyl)pyridine (TFMPBPP), and 2,2 0-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) with various mole ratios of BATB and TFMPBPP ranged from 80/20 to 20/80. All copolyimides were amorphous and had excellent solubility in organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and N,N-dimethylformamide (DMF) at room temperature and displayed good thermal properties with glass transition temperature (T g) of 272 C-338 C, 5% weight loss temperature of 520 C-540 C, and the residue of 44-56% at 750 C in nitrogen. Meanwhile, the T g of the copolymers increased with an increase in the TFMPBPP component. Tough and flexible copolyimide films also exhibited outstanding mechanical properties with tensile strengths of 107.2-153.2 MPa, tensile moduli of 1.4-1.8 GPa, and elongations at break of 13.2-19.6%, low dielectric constants of 2.76-2.92 (1 MHz), and water uptake 0.32-0.62% as well as high optical transparency with the UV cutoff wavelength in the 371-386 nm range and the wavelength of 80% transparency in the range 459-498 nm.
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