Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation

Controlling the reactivity of bonds along polymer chains enables both functionalization and deconstruction with relevance to chemical recycling and circularity. Because the substrate is a macromolecule, however, understanding the effects of chain conformation on the reactivity of polymer bonds emerges as important, yet underexplored. Here, we show how oxy-functionalization of chemically recyclable condensation polymers affects acidolysis to monomers through control over distortion and interaction energies in the rate-limiting transition states. Oxy-functionalization of polydiketoenamines at specific sites on either the amine or triketone monomer segments increased acidolysis rates by over three orders of magnitude, opening the door to efficient deconstruction of linear chain architectures. These insights substantially broaden the scope of applications for polydiketoenamines in a circular manufacturing economy, including chemically recyclable adhesives for a diverse range of surfaces., , , # Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation

[https://doi.org/10.5061/dryad.nk98sf835](https://doi.org/10.5061/dryad.nk98sf835)

## Description of the data and file structure

The archived files include one .ZIP

`calculated_structures`.zip: Coordinates of the molecules used in the multi-path transition state theory calculations for diketoenamine (DKE) acidolysis described in *Theoretical Methods* in the Supplementary information, depicted in Figure 2 of the main text, and analyzed in Figures S1 and S2 of the Supplementary Information. There are two sub-directories: one for the reactant structures and one for the transition state structures. Coordinates are represented in the XYZ file format and are the final coordinates obtained from geometry optimization in Gaussian16 at the *ω*b97XD/6-311+G(d,p) level of theory with the solvent represented implicitly by the solvent model with density (SMD).

* `./reactants`
* This directory contain...