In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk method exhibits exceptional efficiency,...

We report a straightforward and scalable method for the generation of polystyrene-based vinylogous urethane vitrimers using conventional radical polymerization. The copolymerization commercially available inexpensive monomers styrene (2-acetoacetoxy)ethyl methacrylate produced β-ketoester-functional network precursors on multigram scale, which could be cross-linked with diamines to yield thermally robust vitrimer materials. Vitrimers were (re)processed over three destruction/compression...

Polymeric materials comprised of all-carbon backbones are ubiquitous to modern society due their low cost, impressive robustness, and unparalleled physical properties. It is well-known that these often persist long beyond intended usage lifetime, resulting in environmental accumulation plastic waste. A substantial barrier the breakdown polymers relative chemical inertness carbon-carbon bonds within backbone. Herein, we describe a photocatalytic strategy for cleaving carbon-based polymer...

Abstract We demonstrate that electrochemical‐induced decarboxylation enables reliable post‐polymerization modification and degradation of polymers. Polymers containing N ‐(acryloxy)phthalimides were subjected to electrochemical under mild conditions, which led the formation transient alkyl radicals. By installing these redox‐active units, we systematically modified pendent groups chain ends polyacrylates. This approach enabled production poly(ethylene‐ co ‐methyl acrylate) poly(propylene‐...

Single-electron transfer (SET)-induced decarboxylative backbone radical generation was exploited to produce statistical olefin-acrylate copolymers. Quenching of the with an H atom donor yielded ethylene or propylene repeat units.

We report on a fundamental feature of photoiniferter polymerizations mediated with trithiocarbonates and xanthates. The were found to be highly dependent the activated electronic excitation iniferter. Enhanced rates polymerization greater control over molecular weights observed for trithiocarbonate- xanthate-mediated when n → π* transition iniferter was targeted compared activating π transition. disparities in attributed increased rate C–S photolysis which confirmed using model trapping...

We describe a methodology of post-polymerization functionalization to enable subsequent bulk depolymerization monomer by utilizing mechanochemical macro-radical generation. By harnessing ultrasonic chain-scission in the presence N-hydroxyphthalimide methacrylate (PhthMA), we successfully chain-end functionalize polymers promote bulk, achieving up 82 % poly(methyl methacrylate) (PMMA) and poly(α-methylstyrene) (PAMS) within 30 min. This method yields high-purity that can be repolymerized....

This study demonstrates that selective macromolecular electrolysis can be achieved on copolymers containing redox-orthogonal targets by controlling the externally applied voltage. We designed macromolecules phthalimide (E1/2 = -1.8 V vs Ag/AgNO3) and tetrachlorophthalimide -1.3 (meth)acrylates have significantly different reduction potentials such they are separately redox-addressable. The polymer-centered radicals generated decarboxylation either undergo (1) hydrogen atom transfer to form...

This study introduces a novel approach to depolymerize polystyrene in the absence of solvent at significantly reduced temperatures through incorporation thermally labile comonomer. Specifically, we employ N-(methacryloxy)phthalimide (PhthMA) as comonomer with an activated ester capable triggered decarboxylation. Thermal treatment enables generation backbone radicals that promote β-scission and subsequent unzipping. These analogs up 91% reversion monomer under 2 h lower than those required...

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 be externally monitored, intrinsic scalability. Despite these desirable features the recent resurgent use small-molecule electrochemical reactions, development electrolysis has been limited. Herein, we highlight examples driven by heterogeneous...

Thermoresponsive polymer assemblies are of growing interest in fields ranging from photonics to drug delivery, with their phase transitions often attributed upper- or lower-critical solution temperatures and cloud-point behaviors. However, the direct imaging these nanoscale remains underexplored. This study addresses that gap by developing a temperature-sensitive inverse microemulsion system elucidating its dynamic structural under heating. We present composed nonionic surfactants Brij 010...

Abstract We describe a methodology of post‐polymerization functionalization to enable subsequent bulk depolymerization monomer by utilizing mechanochemical macro‐radical generation. By harnessing ultrasonic chain‐scission in the presence N ‐hydroxyphthalimide methacrylate (PhthMA), we successfully chain‐end functionalize polymers promote bulk, achieving up 82 % poly(methyl methacrylate) (PMMA) and poly(α‐methylstyrene) (PAMS) within 30 min. This method yields high‐purity that can be...

In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol% phthalimide ester-containing monomers during polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk method exhibits exceptional efficiency,...

Abstract We demonstrate that electrochemical‐induced decarboxylation enables reliable post‐polymerization modification and degradation of polymers. Polymers containing N ‐(acryloxy)phthalimides were subjected to electrochemical under mild conditions, which led the formation transient alkyl radicals. By installing these redox‐active units, we systematically modified pendent groups chain ends polyacrylates. This approach enabled production poly(ethylene‐ co ‐methyl acrylate) poly(propylene‐...