Thermochemical Approach for Screening of Alternative Metal Oxides as a Flame Retardant of Modacrylic Fiber

Abstract In the view of the exploring novel flame retardants for polymers, modacrylic fibers, which consist of acrylonitrile and vinylidene dichloride, containing metal oxide have been investigated by thermogravimetric–mass spectrometry (TG-MS) analysis. It was found that, among the examined oxides, germanium and antimony oxides formed the corresponding volatile chlorides through the reactions of oxides with hydrogen chloride formed during thermal decomposition of the polymer. The results have been discussed in the framework of thermochemistry. Based on the equilibrium calculation of the polymer–oxide mixture, the predominance diagrams of the M-O-Cl systems (M = Sb and Ge) show that the chlorides are the most stable phases at 573 K, at which temperature the major decomposition of the polymer starts. These results suggest that GeO₂ would be a possible candidate of a flame retardant for chlorinated polymers. However, combustion experiments revealed an insufficient performance of the oxide. The inductively coupled plasma with atomic emission spectroscopy (ICP-AES) analysis showed the reactivity of GeO₂ for HCl was inferior to that of Sb₂O₃, and X-ray fluorescence spectrometer (XRF) analysis of the solid thermal decomposition products showed that the evaporation of germanium was less intense than that of the conventional antimony system. This result is presumably due to the smaller rate of the chlorination of GeO₂ than that of Sb₂O₃.