Solid Products from Thermal Decomposition of Polyethylene Terephthalate: Investigations by CP/MAS 13C NMR and Fourier Transform-IR Spectroscopy

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Journal of Polymer Science: Part A, Polymer Chemistry

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The solid reaction products from pyrolysis of polyethylene terephthalate in the presence and absence of red phosphorus were characterized by CP/MAS 13C‐NMR, FR‐IR, and MAS 31P‐NMR spectroscopy. Over the temperature range of 300–400°C, polyethylene terephthalate was converted in a sealed vial to a highly crosslinked polymer of terephthalic acid. Pyrolysis in the presence of red phosphorus, which functions as a flame retardant by increasing the amount of char, yielded an intractible [sic] polyaromatic phosphate ester. After thermal cleavage of polyethylene terephthalate with formation of free carboxyl and vinyl ester groups, there are two competing reaction pathways. The smaller molecular weight fragments may enter the vapor phase where they undergo further degradation primarily to CO2, CO, and acetaldehyde, as described by others. However, if volatilization of the oligomeric fragments is inhibited, an alternate reaction pathway gives rise to the formation of highly crosslinked char. Red phosphorus decreases the volatility of the oligomeric fragments by converting them to phosphates and thereby enhances char formation.


Journal of Polymer Science: Part A, Polymer Chemistry, Vol. 22, No. 4 (April 1984): 945-957. DOI.