Synthesis of novel poly(phthalazinone fluorenyl ether ketone ketone)s with improved thermal stability and processability
In this study, a series of poly(phthalazinone fluorenyl ether ketone ketone) (PPFEKK) copolymers were designed and synthesized via nucleophilic aromatic substitution polymerization of 1,4-bis(4-fluorobenzoyl)benzene (BFBB), 4-(4-hydroxyphenyl)(2 H)-phthalazin-1-one (DHPZ) and 9,9-bis(4-hydroxyphenyl)fluorene (BHPF) to investigate the effects of bulky fluorene units on the processability and thermal degradation behavior of the polymers. The structures of the PPFEKKs were investigated and confirmed by FTIR, 1 H NMR, wide-angle X-ray diffraction (WAXD) and gel permeation chromatography (GPC) techniques. Traditional thermal measurements showed that the T d 5% and T d 10% values of the copolymers increased as the content of BHPF units increased from 0 to 100 mol%, while their glass transition temperatures gradually decreased. The rheological measurements showed that the processability of the copolymers significantly improved upon incorporation of BHPF units; the poly(aryl ether)s were less viscous and thus more processable. The thermal degradation kinetics were clarified using TGA with Kissinger’s method. The copolymer undergoes two thermal degradation processes: as the content of BHPF units in the copolymers increased from 0 to 100 mol%, the activation energy of the first degradation reaction increased from 228 to 254 kJ mol −1 , and the activation energy of the second degradation reaction increased from 271 to 298 kJ mol −1 . The resulting films displayed excellent tensile strength (higher than 76 MPa), and their Young’s modulus values were inversely proportional to their BHPF contents. Dynamic mechanical analysis showed storage modulus values at 30 °C of approximately 2662, 2826, 2698, 2791 and 2830 MPa for the prepared polymers. Furthermore, the PPFEKKs were soluble in a variety of organic solvents, making them suitable for film casting.
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