Mechanochemical Degradation of Denpols: Synthesis and Ultrasound-Induced Chain Scission of Polyphenylene-Based Dendronized Polymers

New polyphenylene-based dendronized polymers (denpols), exhibiting extended and rigid conformations, were prepared using ring-opening metathesis polymerization (ROMP). Their mechanochemical degradation was explored in ultrasound-induced elongational flow fields. Degradation rate constants were obtained for polyphenylene-based denpols, of varying generation, across a degree of polymerization (DP) range of ∼100–600. In general, it was found that larger side chains led to increased degradation rates and that the rate enhancement was proportional to the natural log of persistence length (Ln­(l p)) or the square root of monomer molecular weight (M mon 0.5). These relationships led to the generation of “master curves” in which the rate constant trends for each polymer series converged, enabling accurate prediction of degradation rate constants for related polymers bearing long alkyl chains or ester-type dendrons. Furthermore, we observed evidence for, and used computational modeling to support, polymer chains undergoing multiple scissions during a single elongation event, leading to faster degradation of daughter fragments that come from parent polymers with large side chains.