Low-Temperature Pyrolysis of Aliphatic Polymers Using a Fluorinated Amorphous Silica-Alumina: Cooperative Reactivity...

Fluorinated amorphous silica-alumina (F-ASA) prepared by the thermolysis of Krossing's Al(OC(CF₃)₃)₃(PhF) Lewis superacid supported on silica is a very reactive catalyst that promotes the pyrolysis (cracking) of aliphatic polymer melts to produce low molecular weight hyperbranched oils. Initial spectroscopic studies reported previously (Gao, J.; Perras, F. A.; Conley, M. P. J. Am. Chem. Soc. 2025, 147, 18145-18154) showed that this material contains a distribution of four-, five-, and six-coordinate aluminum sites and a small amount of Brønsted acid sites, similar to typical amorphous silica-alumina materials that are far less reactive in the pyrolysis of aliphatic polymer melts. The objective of this study was to determine whether other active sites present in F-ASA could facilitate pyrolysis reactions. This study provides evidence for the presence of a redox-active silicon oxycarbide persistent radical ((≡Si)₃C•) in F-ASA. Mims ENDOR EPR experiments show that (≡Si)₃C• is located close to aluminum. Contacting F-ASA with thianthrene (Th) results in oxidation to form the [Th^•+][F-ASA] ion-pair, while reactions with 1-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOH) result in H atom transfer to form TEMPO radical and F-ASA-H containing a mildly acidic (≡Si)₃C-H. Poisoning studies show that both Lewis acidity and (≡Si)₃C• are required for polymer pyrolysis reactivity. We propose that F-ASA promotes the formation of alkyl radicals in polymer melts, which are key intermediates in the thermal pyrolysis reactions of aliphatic polymers, involving the cooperative reactivity of both the Lewis acid and (≡Si)₃C•.