Head-to-Tail and Head-to-Head Molecular Chains of Poly(p-Anisidine): Combined Experimental and Theoretical Evaluation

Abstract

Poly(p-anisidine) (PPA) is a polyaniline derivative presenting a methoxy (-OCH₃) group at the para position of the phenyl ring. Considering the important role of conjugated polymers in novel technological applications, a systematic, combined experimental and theoretical investigation was performed to obtain more insight into the crystallization process of PPA. Conventional oxidative polymerization of p-anisidine monomer was based on a central composite rotational design (CCRD). The effects of the concentration of the monomer, ammonium persulfate (APS), and HCl on the percentage of crystallinity were considered. Several experimental techniques such as X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), multifractal analysis, Nuclear Magnetic Resonance (¹³C NMR), Fourier-transform Infrared spectroscopy (FTIR), and complex impedance spectroscopy analysis, in addition to Density Functional Theory (DFT), were employed to perform a systematic investigation of PPA. The experimental treatments resulted in different crystal structures with a percentage of crystallinity ranging from (29.2 ± 0.6)% (PPA1_HT) to (55.1 ± 0.2)% (PPA16_HT-HH). A broad halo in the PPA16_HT-HH pattern from 2θ = 10.0-30.0° suggested a reduced crystallinity. Needle and globular-particle morphologies were observed in both samples; the needle morphology might have been related to the crystalline contribution. A multifractal analysis showed that the PPA surface became more complex when the crystallinity was reduced. The proposed molecular structures of PPA were supported by the high-resolution ¹³C NMR results, allowing us to access the percentage of head-to-tail (HT) and head-to-head (HH) molecular structures. When comparing the calculated and experimental FTIR spectra, the most pronounced changes were observed in ν(C-H), ν(N-H), ν(C-O), and ν(C-N-C) due to the influence of counterions on the polymer backbone as well as the different mechanisms of polymerization. Finally, a significant difference in the electrical conductivity was observed in the range of 1.00 × 10^-9 S.cm^-1 and 3.90 × 10^-14 S.cm^-1, respectively, for PPA1_HT and PPA16_HT-HH.

Keywords: DFT; conjugated polymer; head-to-head; head-to-tail; multifractal analysis; poly(p-anisidine).