Kinetic Analysis of Mechanochemical Chain Scission of Linear Poly(phthalaldehyde)

The kinetics of mechanochemical chain scission of poly(phthalaldehyde) (PPA) are investigated. Ultrasound‐induced cavitation is capable of causing chain scission in the PPA backbone that ultimately leads to rapid depolymerization of each resulting polymer fragment when above the polymer's ceiling temperature ( T c ). An interesting feature of the mechanochemical breakdown of PPA is that “half‐chain” daughter fragments are not observed, since the depolymerization is rapid following chain scission. These features facilitate the determination of rate constants of activation for multiple molecular weights from a single sonication experiment. Additionally, the degradation kinetics are modified with chain‐end trapping agents through variation of the nature and amount of small molecule nucleophile or electrophile.