Structure and properties of halogen-free flame retardant and phosphorus-containing aromatic poly(1,3,4-oxadiazole)s fiber

Abstract

In order to improve the flame retardance of aromatic polyoxadiazole (p-POD) fiber, a series of phosphorus-containing PODs (pho-POD) were synthesized by introducing triaryl phosphine oxide (TPO) units into the main chains of p-POD using hydrazine sulfate, terephthalic acid and bis(p-carboxy)phenyl phosphine oxide (BCPPO) as monomers, and then halogen-free flame resistant pho-POD fibers were obtained from wet spinning. The structure and properties of the pho-POD fibers were characterized and measured in detail using the methods of wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), oxygen bomb calorimeter, Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) etc. The results show that the introduction of TPO units resulted in the weakening of the crystallization ability, the formation of the poriferous and lax interior structure, the slight decrease in the thermal stability and mechanical properties of the POD fibers. However, the value of LOI obviously increased from 28% to 35%, and the gross heat of combustion (GHC) decreased from 19.72 MJ kg⁻¹ to 17.84 MJ kg⁻¹ with the increase in the content of the BCPPO. Moreover, the combustion residue of pho-POD fiber revealed a smooth, dense and non-porous carbon layer, which could effectively play a role of oxygen barrier and enhance the flame resistance. From the above results, it can be concluded that the flame resistance of the POD fiber could be improved significantly after introducing the TPO unit. The results of Py-GC/MS illustrate that the TPO unit of pho-POD could inhibit the production of volatile products, which could be confirmed that the mechanism of enhancing the flame retardancy by introducing TPO units was mainly the flame retardation of the condensed phase.