Depolymerization of Bottlebrush Polypentenamers and Their Macromolecular Metamorphosis

The depolymerization of bottlebrush (BB) polymers with varying lengths of polycyclopentene (PCP) backbone and polystyrene (PS) grafts is investigated. In all cases, ring closing metathesis (RCM) depolymerization of the PCP BB backbone appears to occur through an end-to-end depolymerization mechanism as evidenced by size exclusion chromatography. Investigation on the RCM depolymerization of linear PCP reveals a more random chain degradation process. Quantitative depolymerization occurs under thermodynamic conditions (higher temperature and dilution) that drives RCM into cyclopentenes (CPs), each bearing one of the original PS grafts from the BB. Catalyst screening reveals Grubbs' third (G3) and second (G2) generation catalyst depolymerize BBs significantly faster than Grubbs' first generation (G1) and Hoveyda-Grubbs' second generation (HG2) catalyst under identical conditions while solvent (toluene versus CHCl₃) plays a less significant role. The length of the BB backbone and PS side chains also play a minor role in depolymerization kinetics, which is discussed. The ability to completely deconstruct these BB architectures into linear grafts provides definitive insights toward the ATRP "grafting-from" mechanism originally used to construct the BBs. Core-shell BB block copolymers (BBCPs) are shown to quantitatively depolymerize into linear diblock polymer grafts. Finally, the complete depolymerization of BBs into α-cyclopentenyl-PS allows further transformation to other architectures, such as 3-arm stars, through thiol-ene coupling onto the CP end group. These unique materials open the door to stimuli-responsive reassembly of BBs and BBCPs into new morphologies driven by macromolecular metamorphosis.