Citation: Chun-xia Zhao, Ling Zhao, Xiao-jia He, Hao-lan Gou, Yun-tao Li. Effects of Fluorenyl Polyphosphazene Microspheres on the Flame Retardant Properties of Polybenzoxazine Resins[J]. Acta Polymerica Sinica, ;2018, 0(10): 1336-1344. doi: 10.11777/j.issn1000-3304.2018.18042 shu

Effects of Fluorenyl Polyphosphazene Microspheres on the Flame Retardant Properties of Polybenzoxazine Resins

Department of Materials and Engineering, Southwest Petroleum University, Chengdu 610500

Corresponding author: Chun-xia Zhao, polychem@swpu.edu.cn Yun-tao Li, yuntaoli@swpu.edu.cn
Received Date: 2 February 2018
Revised Date: 29 March 2018
Available Online: 6 September 2018

Fluorenyl polyphosphazene (PZFP) microspheres were facilely prepared through a one-step precipitation copolymerization of hexachlorocyclotriphosphazene (HCCP) and 4,4′-(9-fluorenylidene)diphenol under ultrasonic. PZFP microspheres were incorporated into polybenzoxazine resins to improve the flame properties of the polymers. The results of thermogravimetric analysis (TGA), cone calorimeter (CONE) and dynamic thermal mechanical analysis (DMA) showed that incorporation of PZFP microspheres enhanced the char residues amount of PBa during thermal degradation process, reduced the heat release rate (HRR), delayed the time to ignition (TTI) and increased the fire performance index (FPI) of PBa in fire. Interestingly, PBa/PZFP-10% showed the relatively best flame retardant properties among a series of PBa/PZFP composites with different PZFP contents. In comparison to pure PBa, the HRR value in the composite PBa/PZFP-10% was reduced to 214 kW·m⁻² from 566 kW·m⁻² for pure PBa, and FPI value was enhanced to 0.243 from 0.087. The glass transition temperature (T_g) and storage modules of PBa/PZFP-10% were increased slightly, with the introduction of 10% PZFP microspheres. The T_g of PBa and PBa/PZFP-10% was 222 and 226 °C, respectively. It is believed that PZFP microspheres offered PBa resins good flame retardant properties, without affecting the application temperature of PBa. The char residue analysis using scanning electron microscopy (SEM) suggested the formation of high-quality char layer with compact outer surfaces and polyphorous inner structure. The volatile products formed in the thermal degradation process of PBa and PBa/PZFP composites were detected by a TGA-Fourier transform infrared spectrometer (TGA-FTIR). The improved flame retardancy of PBa/PZFP composites was mainly attributed to a combination of the greatly increased melt viscosity of PBa and matrix fast swelling due to the pyrolytic gases. Additionally, PZFP microspheres was found to greatly reduce the amount of pyrolytic gases containing N―H and ―C＝C＝C― groups. Instead, it released phosphorous-containing species to achieve flame retardancy in the gas phase. PZFP microspheres contributed a synergistic condensed phase and gas phase flame retardant mechanism for PBa resins.
- Fluorenyl polyphosphazene microspheres,
- Flame retardancy,
- Polybenzoxazine resins,
- Cone calorimeter
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