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Currently, the metal-organic framework (MOF) is a promising candidate for flame-retardant polymers. In this study, a Fe-based MOF, MIL-88B(Fe), was introduced to polyethylene terephthalate (PET) and 3-hydroxyphenylphosphinyl-propanoic acid copolymer (P-PET) to reduce the fire hazard involved in using PET. The limiting oxygen indexes (LOIs) of MIL-PET and MIL-P-PET improved by 27% and 30%, respectively. The UL-94 level achieved for MIL-P-PET was V-0 rating. The thermal degradation and carbonization mechanisms of MIL-PET and MIL-P-PET were systematically investigated through thermogravimetric analysis coupled with a Fourier transform infrared spectroscopy (TG-IR), pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), x-ray photoelectron spectroscopy (XPS), and Raman spectrum combined with quantum chemical molecular dynamics simulation. With the addition of MIL-88B(Fe), high graphitization and a hard flammability char residual were generated. Compared with neat PET, the ferric ions efficiently catalyzed the homolytic cleavage and dehydrogenation of PET to produce a large amount of CO 2 and terephthalic acid for MIL-PET in gas phase. Rough and hierarchical char residual with ferric oxide was also generated when temperatures exceeded 600 °C. However, the carbonization process was inhibited due to the coordinated complex between phosphorus and ferric ions in MIL-P-PET, invaliding the decarboxylation and generating more benzoic acid and its precursor, which led to heavy smoke.

Thermal Degradation and Carbonization Mechanism of Fe-Based Metal-Organic Frameworks onto Flame-Retardant Polyethylene Terephthalate