Synthesis And Properties Of Novel Poly(Aryl Ether Ketone)s With Pendant Cyano Groups

In this dissertation,we reviewed the recent development of poly aryl ether ketoneand reported the synthesis and properties of six novel kinds of poly aryl ether ketones" with pendant cyano,groups. A new monomer 2,6—diphenoxybenzonitrile(DPOBN) was prepared by the condensation of 2,6—difluorobenzonitrile with phenol in high boiling solvent NMP. A novel series of poly(ethe ether ketone ketone)/poly(ether ketone ketone)s with pendant cyano groups(C—PEEKK/PEKK) were prepared by low temperature solution polycondensation of DPOBN as the third monomer with diphenyl ether(DPE) and TPC in the presence of AlCl₃/DCE/NMP as complex catalyst/solvent system. The polymers obtained were characterized by IR, DSC, TG, WAXD etc, The results indicate that the copolymers exhibit good heat—resistance and solvent—resistance. The solubility of the polymers enhances while the Tm and the crystallinity of the polymers decrease with the increasing of DPOBN content, the polymers are semi—crystalline when the content of DPOBN is below 50mol%.A new kind of poly (aryl ether ether ketone ketone)s with pendant cyano groups(C—PEEKK) were synthesized by copolycondensation of DPOBN with aromatic diacid chlorides such as terephthaloyl chloride(TPC) and isophthaloyl chloride(IPC) by the same procedure. The results suggest that the polymers are non—crystalline,together with good thermostabilities and can be dissolved in some strong polar non—protonic solvents and that Tg and Td decrease with the raising DPOBN content.According to the literature procedure, a monomer 4,4' — diphenoxy diphenylsulfone(DPODPS) was prepared. A series of poly(ether ether ketone ketone)/poly(ether sulfone ether ketone ketone)s with pendant cyano groups (G—PEEKK/PESEKK) were synthesized by copolycondensation of DPOBN with DPODPS and TPC by the same procedure. The results indicate that the polymers are non—crestalline, together with good thermostabilities and can be well dissolved in more solvents and Td increases with the raising DPODPS content.According to the literature procedure, a monomer 1,4-bis(4-phenoxybenzoyl)benzene(BPOBB) was prepared. A series of poly(ether ether ketone ketone)/poly(eher ketone ketone ether ketone ketone) with pendent cyano groups(C-PEEKK/PEKKEKK) copolymers were synthesized by copolycondensation of DPOBN with BPOBN and TPC by the same procedure. The results indicate that the coplymers obtained are all semi—crystalline and exhibit good heat—resistance and good solvent-resistance.when molar ratios of DPOBN/BPOBK rang from15/85 to 70/30. The Tm of the copolymer decreases with the increasing of DPOBN content.Another new monomer 2,6—bis( β—naphthoxy)benzonitrile(DNOBN) was prepared from β—naphthol and 2,6—difluorobenzonitrile by the procedure similar to DPOBN. A novel series of poly(ether ether ketone ketone)/poly(ether ketone ketone) copolymers with pendant cyano groups and containing naphthalene rings were prepared by the polycondensation of DNOBN with DPE and TPC by the same procedure. The results indicate that the copolymers exhibit excellent heat — resistance.The Tg of the copolymers increases while the the Tm and the crystallinity of the copolymer decrease with the increasing of DNOBN content, the copolymers are semi—crystalline when the content of DNOBN is below 25mol%.A series of poly(ether ether ketone ketone)/poly(ether ketone ketone ether ketone ketone) copolymers with pendant cyano groups and containing naphthalene rings were prepared by the polycondensation of DNOBN with BPOBB and TPC by the same procedure. The results indicate that the copolymers exhibit excellent heat—resistance and good solvent—resistance, only when the content of DNOBN is above 20mol%, the copolymers can be dissolved or swelled in some strong polar non—protonic solvents such as NMP, DMF, DMSO,etc. The Tg of the copolymers increases while the Tm and the crystallinity of the copolymers decrease with the increasing of DNOBN content.