Chemical and electrochemical synthesis of conducting graft copolymer of acrylonitrile with aniline

Abstract

A new conducting copolymer, polyacrylonitrile-graft-polyaniline (PAN-g-PANi), has been prepared by chemical and electrochemical methods from a precursor polymer. Poly[acrylonitrile-co-(acrylimine phenylenediamine)] (PAN-co-PAIPD) was synthesized chemically by reacting PAN with sodium 1,4phenylenediamine salt. PAN-g-PANi was synthesized chemically using ammonium peroxydisulfate as the oxidant and p-toluenesulfonic acid in dimethylsulfoxide solution and adding aniline to oxidized PAN-co-PAIPD. Electrochemical polymerization was carried out by spin coating PAN-co-PAIPD on the surface of a Pt electrode, then the growth of the graft copolymer (PAN-g-PANi) in the presence of fresh aniline and acidic solution. The structures of the graft copolymer and PAN-co-PAIPD were characterized using UV-visible, Fourier transform infrared, and 1 H and 13 C NMR spectroscopies. The thermal properties of PAN-g-PANi were studied using thermogravimetric analysis and differential scanning calorimetry. Scanning electron microscopy (SEM) images showed that the morphology of PAN-g-PANi copolymer films was homogeneous. Electrical conductivity of the copolymer was studied using the four-probe method, which gave a conductivity of 4.5 × 10 −3 S cm −1 with 51.4% PANi. SEM and electrical conductivity measurements supported the formation of the graft copolymer.

New Crystalline Aniline and o-Anthranilic Acid Copolymer/Kaolinite Composites

“…It was reported that, the weak mechanical properties of conductive polymers could be improved by this way [11][12][13] . Clay minerals, such as montmorillonite and bentonite, were much more preferred among non-conductive materials for their properties such as big surface area, high ion exchange capacity, natural abundance and cheapness [14][15][16] .…”

Two-Dimensional Texture of Intrinsic Conductive Poly(styrene-co-maleanilic Acid) Grafted with Polyaniline: Formation and Conductivity

“…Literature review on PANI-polymer and ICP-polymer systems show that these regimes are widely employed to modulate solution processibility, film morphology, band-gap tunning, and therefore improve their ability for electron=energy transport and luminescence. Although numerous PANI-containing polymers have been reported by blending technique, only a few cases involved grafting PANI onto a polymer backbone or grafting a polymer onto a PANI backbone [30][31][32]36,37]. Successful formation of PANI-polymer polyblend systems relies basically on a variety of electrostatic and hydrophobic interactions, such as H-bonding, Van der Waal and p-stacking, and therefore suffers from several drawbacks such as segregation=aggregation, inhomogeneous distribution, poor domain-packing, and others [38][39][40].…”

“…Consequently, the resulting grafted biomaterials find several biomedical and pharmaceutical applications. Furthermore, grafting ICPs onto bioactive colloidal systems is an attractive practical method, not only for the formation of novel bio-functional materials but also for extending their applications into sensors, actuators, smart fabrics, and biochemical=biomechanical (tissue engineering, drug delivery) devices [22,27,[30][31][32].…”

“…In recent years, several research groups have devoted significant effort to modify the structure of PANI with the goal of tuning its chemical, electrochemical, optical, mechanical, processibility and biocompatibility [28][29][30][31][32][33][34][35]. Literature on structural modifications of PANI includes functionalization, metallization, and copolymerization with a variety of common organic polymers and rubbers and composite formation with inorganic frameworks (heteropolyacids, polyoxometallate, SiO 2 , SnO 2 , siloxanes, etc.).…”

Chemical modification of nano-structured polyaniline by N-grafting of hexadecylbromide

“…Conducting polyaniline exhibits extraordinary electronic properties, such as low ionization potential and high electron affinity as a result it can be easily reduced or oxidized. Because of this, polyaniline finds a wide variety of applications in batteries, electromagnetic devices, sensors, light-emitting diodes, and electromagnetic shielding [2][3][4][5]. Polyaniline is a particularly attractive material owing to its good stability, easy synthesis, and desirable conductivity.…”