Synthesis and spectroscopic characterization of polymer and oligomers of ortho-phenylenediamine

• Published in: European polymer journal Vol. 46; no. 3; pp. 484 - 493
• Main Authors: Sestrem, Ricardo H., Ferreira, Daniela C., Landers, Richard, Temperini, Marcia L.A., do Nascimento, Gustavo M.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01-03-2010; Elsevier
• Subjects: Applied sciences; Conducting polymers; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polyaniline; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; Raman spectroscopy; XANES; Conducting polymers; Raman spectroscopy; Polyaniline; XANES; Trimer; Aniline derivative polymer; Molecular structure; Cyclopolymerization; Aromatic polymer; Peroxodisulfates; Oligomer; Experimental study; Ladder polymer; Phenylenediamine; Nitrogen heterocycle polymer; Cyclopolymer; Preparation; Dimer; Oxidative polymerization
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/j.eurpolymj.2009.12.007

Poly(
ortho-phenylenediamine) and oligomers of
ortho-phenylenediamine were characterized by Raman, FTIR, UV–vis, X-ray absorption, XPS, EPR, MALDI spectroscopies. It was determined that the polymer is constituted by phenazinic and quinonediimine segments with different protonation levels.
Poly(
ortho-phenylenediamine) and oligomers of
ortho-phenylenediamine were chemically synthesized and characterized by UV–vis,
1H and
13C NMR, FTIR and resonance Raman spectroscopies. Polymerization of
ortho-phenylenediamine in HCl medium with ammonium persulfate only leads the trimer compound, in disagreement with some previous reports. Nevertheless, in acetic acid medium it was possible to prepare a polymer constituted by ladder phenazinic segments with different protonation levels and quinonediimine rings (polyaniline-like). X-ray absorption at N K-edge (N K XANES), X-ray photoelectron (XPS) and Electron paramagnetic resonance (EPR) spectroscopies were used to determine the different kinds of nitrogen presents in this class of polymer. N K XANES spectrum of poly(
ortho-phenylenediamine) shows the band of
N
nitrogen of non-protonated phenazinic rings at 398.2
eV. In addition, XPS and N K XANES data confirm the presence of different types of protonated nitrogens in the polymeric poly(
ortho-phenylenediamine) chain and the EPR spectrum shows that the polymer has a very weak polaronic signal.