Dithiocarbamate-mediated controlled copolymerization of ethylene with cyclic ketene acetals towards polyethylene-based degradable copolymers

In this article, degradable polyethylene (PE)-based copolymers containing ester units in the backbone were prepared through the hybrid copolymerization of ethylene and cyclic ketene acetals (CKAs) mediated by dithiocarbamate successfully.

Unraveling the History and Revisiting the Synthesis of Degradable Polystyrene Analogues via Radical Ring-Opening Copolymerization with Cyclic Ketene Acetals

Degradable analogues of polystyrene are synthesized via radical ring-opening (co)polymerization (rROP) between styrene and two cyclic ketene acetals, namely 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO). This approach periodically inserts ester bonds throughout the main chain of polystyrene, imparting a degradation pathway via ester hydrolysis. We discuss the historical record of this approach, with careful attention paid to the conflicting findings previously reported. We have found a common 1H NMR characterization error, repeated throughout the existing body of work. This misinterpretation is responsible for the discrepancies within the cyclic ketene acetal (CKA)-based degradable polystyrene literature. These inconsistencies, for the first time, are now understood and resolved through optimization of the polymerization conditions, and detailed characterization of the degradable copolymers and their corresponding oligomers after hydrolytic degradation.

The Radical Ring-Opening Polymerization of Cyclic Ketene Acetals Revisited: An Experimental and Theoretical Study

Radical Ring-Opening polymerization (rROP) of Cyclic Ketene Acetals (CKAs) combines the advantages of both ring-opening and radical polymerization thereby allowing the robust production of polyesters. In this article we investigate in detail the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict <i>in silico</i> the ring-opening ability of CKA monomers<br>

The Radical Ring-Opening Polymerization of Cyclic Ketene Acetals Revisited: An Experimental and Theoretical Study

Radical Ring-Opening polymerization (rROP) of Cyclic Ketene Acetals (CKAs) combines the advantages of both ring-opening and radical polymerization thereby allowing the robust production of polyesters. In this article we investigate in detail the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict <i>in silico</i> the ring-opening ability of CKA monomers<br>

Reversible-deactivation radical polymerization of cyclic ketene acetals

This review discusses the history of reversible-deactivation radical ring-opening polymerization of cyclic ketene acetals, focusing on the preparation of degradable complex polymeric architectures.

DFT-calculation-assisted prediction of the copolymerization between cyclic ketene acetals and traditional vinyl monomers

The ring-opening polymerization of cyclic ketene acetals (CKAs) and vinyl monomers is an elegant method to produce degradable copolymers. Owing to DFT calculations, we are now able to better understand the reactivity of CKAs & common vinyl monomers.

Novel monomers in radical ring-opening polymerisation for biodegradable and pH responsive nanoparticles

We report the first amine-bearing cyclic ketene acetals (CKAs) for radical ring-opening polymerisation (RROP). The resulting polyesters and their corresponding nanoparticles were biodegradable and showed the desired pH sensitive behaviour.

Phosphonium ylide catalysis: a divergent diastereoselective approach to synthesize cyclic ketene acetals [thia(zolidines/zinanes)] from β-ketothioamides and dihaloalkanes

Phosphonium ylides are being reported here as a catalyst for the formation of thiazolidines and 1,3-thiazinanes from β-ketothioamides with dihaloalkanes via [3 + 2] and [3 + 3] annulations under metal-free conditions.