Abstract
Phosphonated polyanilines were synthesized by copolymerization of aniline (ANI) with both 2- and 4-aminophenylphosphonic acids (APPA). The material composition and the final properties of the copolymers can be easily tailored by controlling the monomers ANI/APPA molar feed ratio. An important influence on the reactivity of monomers has been found with the substituent position in the ring, leading to differences in the properties and size of blocks of each monomer in the polymer. As expected, while 2APPA shows more similarities to ANI, 4APPA is much less reactive. Phosphorus loading of ~5 at% was achieved in the poly(aniline-co-2-aminophenylphosphonic acid) (PANI2APPA) with a 50/50 molar feed ratio. All the resulting copolymers were characterized by different techniques. Experimental results and density functional theory (DFT) computational calculations suggest that the presence of phosphonic groups in the polymeric chain gives rise to inter- and intra-chain interactions, as well as important steric effects, which induce a slight twist in the substituted PANI structure. Therefore, the physicochemical, electrical, and electrochemical properties are modified and can be suitably controlled.
Highlights
−1 around 1214 cm is observed in PANI2APPA (50/50), which could be ascribed to P=O stretching not observed in theisother copolymer due to the lower
Thin films of PANI and PANIAPPA copolymers were deposited onto a glassy carbon (GC)
The first redox process clearly appears in all copolymers, the peak potential is shifted to more positive potentials than in the PANI as the amount of P-loading increases, at around 30, 40, and 100 mV for PANI4APPA (50/50), PANI2APPA (80/20), and PANI2APPA (50/50), respectively
Summary
Polyaniline (PANI) stands as one of the most attractive and revolutionary conjugated conducting polymers (CPs), which has led to an intense scientific research since its discovery in the 1980s [1,2]. Steric effects may result in a total hindrance to the homopolymerization of substituted monomers To overcome these concerns, copolymerization with aniline is considered as a key alternative, in which the material composition and the final properties can be tailored by a suitable controlling of the monomers ratio in the feed solution [16,19,20]. Copolymerization with aniline is considered as a key alternative, in which the material composition and the final properties can be tailored by a suitable controlling of the monomers ratio in the feed solution [16,19,20] In this sense, it is of great importance to consider the relative reactivity of each monomer and the influence of the substituent position in the ring, in order to more accurately predict the degree of modification of the resulting copolymer [19]. Density functional theory (DFT) computational calculations were performed for a better understanding of the distribution of monomers in the polymer structure and the effect of phosphorus functionalities on its physicochemical, electrical, and electrochemical properties
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