Mechanically Triggered Polymer Deconstruction through Mechanoacid Generation and Catalytic Enol Ether Hydrolysis.

Polymers that amplify a transient external stimulus into changes in their morphology, physical state, or properties continue to be desirable targets for a range of applications. Here, we report a polymer comprising an acid-sensitive, hydrolytically unstable enol ether backbone onto which is embedded gem -dichlorocyclopropane ( g DCC) mechanophores through a single postsynthetic modification. The g DCC mechanophore releases HCl in response to large forces of tension along the polymer backbone, and the acid subsequently catalyzes polymer deconstruction at the enol ether sites. Pulsed sonication of a 61 kDa PDHF with 77% g DCC on the backbone in THF with 100 mM H 2 O for 10 min triggers the subsequent degradation of the polymer to a final molecular weight of less than 3 kDa after 24 h of standing, whereas controls lacking either the g DCC or the enol ether reach final molecular weights of 38 and 27 kDa, respectively. The process of sonication, along with the presence of water and the existence of g DCC on the backbone, significantly accelerates the rate of polymer chain deconstruction. Both acid generation and the resulting triggered polymer deconstruction are translated to bulk, cross-linked polymer networks. Networks formed via thiol-ene cross-linking and subjected to unconstrained quasi-static uniaxial compression dissolve on time scales that are at least 3 times faster than controls where the mechanophore is not covalently coupled to the network. We anticipate that this concept can be extended to other acid-sensitive polymer networks for the stress-responsive deconstruction of gels and solvent-free elastomers.