Thermal Analysis of Acrylonitrile Polymerization and Cyclization in the Presence of N,N-Dimethylformamide

This paper examines the polymerization of acrylonitrile to poly(acrylonitrile)(PAN), and its cyclization, in bulk form and using N,N-dimethylformamide (DMF) as solvent in which both monomer and polymer are soluble. Thermal analysis of the resultant products after polymerization has been performed by DSC and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Scanning electron microscopy has been used to study the morphology of the resultant products and after thermal treatments. The DSC thermal curve of PAN-DMF sample is quite different from the PAN bulk sample, showing a single sharp exothermic peak associated with nitrile group polymerization (cyclization) of PAN at lower temperature (240°C) than that of bulk PAN sample (314°C). Cyclization of PAN was confirmed by IR spectroscopy. It was found that the amide molecules are difficult to eliminate completely in the product obtained after the polymerization reaction, even after prolonged heating at 110°C, and remain occluded. The formation of a complex by dipolar bonding is also possible and it is discussed. It is concluded that the amount of heat evolved as well as the temperature interval over which it is released are influenced by the chemical processing of PAN when using DMF as solvent of both monomer and polymer. Pyrolysis of these PAN samples revealed the release of occluded molecules of DMF, and several compounds containing nitrogen produced from the thermal degradation processes. All these results are interesting to know the chemical processing of carbon fibres and activated carbon fibres from PAN modified precursors.This revised version was published online in November 2005 with corrections to the Cover Date.