Selective Electrochemical Modification and Degradation of Polymers.

We demonstrate that electrochemical-induced decarboxylation enables reliable post-polymerization modification and degradation of polymers. Polymers containing N-(acryloxy)phthalimides were subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. By installing these redox-active units, we systematically modified the pendent groups and chain ends of polyacrylates. This approach enabled the production of poly(ethylene-co-methyl acrylate) and poly(propylene-co-methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. Spectroscopic and chromatographic techniques reveal these transformations are near-quantitative on several polymer systems. Electrochemical decarboxylation also enables the degradation of all-methacrylate poly(N-(methacryloxy)phthalimide-co-methyl methacrylate) copolymers with a degradation efficiency of >95 %. Chain cleavage is achieved through the decarboxylation of the N-hydroxyphthalimide ester and subsequent ß-scission of the backbone radical. Electrochemistry is thus shown to be a powerful tool in selective polymer transformations and controlled macromolecular degradation.

Electrochemical Postpolymerization Modification and Deconstruction of Macromolecules.

Electrolysis is an emerging approach to polymer postpolymerization modification, deconstruction, and depolymerization. Electrochemical reactions are particularly appealing for macromolecular transformations because of their high selectivity, ability to be externally monitored, and intrinsic scalability. Despite these desirable features and the recent resurgent use of small-molecule electrochemical reactions, the development of macromolecular electrolysis has been limited. Herein, we highlight recent examples of polymer transformations driven by heterogeneous redox chemistry. Throughout our exploration of macromolecular electrolysis, we provide our perspective on opportunities for continued investigation in this nascent field. Specifically, we highlight how targeted reaction development through deeper mechanistic insight will expand the scope of materials that can be (de)constructed with electrochemical methods. As this insight is developed, we expect macromolecular electrolysis to emerge as a high-functioning and complementary tool for macromolecular functionalization and deconstruction.

Electroactive Ionic Polymer of Intrinsic Microporosity for High-Performance Capacitive Energy Storage.

Here, an ionic polymer of intrinsic microporosity (PIM) as a high-functioning supercapacitor electrode without the need for conductive additives or binders is reported. The performance of this material is directly related to its large accessible surface area. By comparing electrochemical performance between a porous viologen PIM and a nonporous viologen polymer, it is revealed that the high energy and power density are both due to the ability of ions to rapidly access the ionic PIM. In 0.1 m H2SO4 electrolyte, a pseudocapacitve energy of 315 F g-1 is observed, whereas in 0.1 m Na2SO4, a capacitive energy density of 250 F g-1 is obtained. In both cases, this capacity is retained over 10 000 charge-discharge cycles, without the need for stabilizing binders or conductive additives even at moderate loadings (5 mg cm-2). This desirable performance is maintained in a prototype symmetric two-electrode capacitor device, which has >99% Coloumbic efficiency and a <10 mF capacity drop over 2000 cycles. These results demonstrate that ionic PIMs function well as standalone supercapacitor electrodes and suggest ionic PIMs may perform well in other electrochemical devices such as sensors, ion-separation membranes, or displays.