An innovative method for highly-efficient fabrication of carbon fiber precursors via acrylonitrile emulsion copolymerization coupled to a chemical oscillator

A new synthetic protocol to produce the carbon fiber precursor polyacrylonitrile (PAN) and its block copolymers with polyethylene glycol (PEG) is proposed here. The constant flux of radical species produced at low concentrations during the oscillating Belousov-Zhabotinsky (BZ) reaction was properly exploited to initiate the radical polymerization reaction. Compared with conventional methods, this oscillating initiation decreases the probability of chain termination, thus favouring the production of high molecular weight polymers, and it does not require an inert atmosphere and elevated temperatures to be produced. The solubility of the polymeric chains during the polymerization reaction was improved by adding the anionic micelle-forming surfactant sodium dodecyl sulphate (SDS). Following the initiation step, short oligomer chains are able to overcome the micellar interface, thereby reaching a favourable environment for the increase of the polymeric chains, thus strongly contributing to the increase of the molecular weight of the fibers' precursors. The synthesis was conducted by adding the monomer acrylonitrile (AN) to the unperturbed and PEG-perturbed BZ system after the onset of the oscillations, in the absence and presence of increasing amounts of the SDS surfactant. The potentiometric technique was utilized to detect the dynamics of the oscillatory reaction. Preliminarily, the response of the BZ system to the monomer addition was investigated. Additional information was provided from the study of the effect of the SDS and PEG concentration on the dynamics of the BZ reaction during AN polymerization, thus obtaining a deepening in the understanding of the BZ mechanism. The characterization of the obtained polymers and copolymers, by melting point measurements, molecular weight determinations, Fourier Transform Infrared (FTIR), X-ray diffraction (XRD) analyses, and thermal treatments, indicated that the proposed synthetic method produces carbon fiber precursors with high molecular weight and good thermal stability. The addition of the surfactant was revealed as a good method to improve and/or finely tune the precursor molecular weight. The proposed synthetic protocol represents a valuable alternative to conventional methods to produce highperformant precursors of carbon fibers.