Meta-poly(phthalazinone ether ketone ketone) copolymers with 4,4′-dihydroxybiphenyls (meta-PPBEKK) was synthesized with 4,4′-dihydroxybiphenyls (BP), 1,3-bis(4-fluorobenzoyl)benzene (meta-DFKK) and 4-(4-hydroxyphenyl)-2,3-diazaphthalene-1-one (DHPZ). The copolymers are high-temperature resistant and have good solubility in many solvents. With increasing molar ratio of BP to meta-DFKK from 0 to 0.2, the addition of BP improves number-average molecular masses, intrinsic viscosity, mechanical properties and fluidity of meta-PPBEKKs. When the molar ratio of BP to meta-DFKK is 0.2, the intrinsic viscosity reaches 1.14 dL g−1, the number-average molecular mass reaches 44700 g mol−1, the maximum thermal elongation ratio reaches 14 with strength of 127.1 MPa and Young’s modulus of 2.4 GPa. With increasing molar ratio of BP to meta-DFKK from 0 to 0.2, meta-PPBEKKs have improved comprehensive properties, and make sense in many fields.
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