Study On Synthesis, Structure And Properties Of Novel Fluorine-containing Poly(amide-sulfonamide)s

Polyamides are classical polymers and have been studied intensively ever since their discovery by Carothers in 1934,because of their relatively high modulus, toughness and strength, low creep and good temperature resistance. Copolymerization greatly increased the ability of polymer scientists to tailor-make polymers with specifically desired properties. Sulfonamides, which are known for their biological activity and also be used as sorbents of metal ions, chelating agents and in self-assembly, might act an interesting copolymerization part. However, to our knowledge, polymers which contain both amide and sulfonamide linkages, as well as carbon-fluorine bonds have not been reported before.We specially synthesized and applied a cyclic fluorine-containing monomer namedβ-hydroxytetrafluoroethanesulfonic acid sultone (TFE-sultone), which can be catalyzed to isomerize into a bi-functional compound containing acyl fluoride and sulfonyl fluoride at each end. Therefore we successfully synthesized fluoropoly(amide-sulfonamide)s (F-PASAs) by the reaction of hexamethylenediamine, 1,4-benzenediamine, 1,3-benzenediamine, Zn(o-PDA)Cl2 and Cd(o-PDA)Cl2 with TFE-sultone, achieving amidation simultaneously with sulfonamidation.A general method to synthesis F-PASAs was set up through analyzing and comparing the interfacial method and solution method on the reaction using hexamethylenediamine. The chemical structures of the obtained F-PASAs were characterized by intrinsic viscosity measurements, GPC, FTIR, 1H NMR, 19F NMR and element analysis in detail. Thermal properties and optical property of F-PASAs were investigated by DSC, DMA, TGA and UV-vis spectra, respectively. F-PASAs-S possess good thermostability, high transparency and compatibility with nylons.The sequential alignment of these co-present functional groups along polymer main chain was clearly confirmed by variable temperature 1H NMR and 19F NMR study on 1,4-benzenediamine based fluoropoly(amide-sulfonamide)s. Various kinds of hydrogen bonds, including the special N-H…F-C, and N-H…O=C, N-H…O=S=O hydrogen bonding, were discovered in a different perspective that through two-dimensional correlation IR spectroscopy method. O-phenylenediamine and its Cd2+ coordination-complex based fluoropoly(amide-sulfonamide)s show high fluorescence quantum yields of 0.65 in DMSO solution,which possess potential in optical applications, while that of Zn2+ coordination-complex based ones is 0.39.