Data from: Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation
Data files
Dec 19, 2024 version files 318.40 KB
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calculated_structures.zip
315.81 KB
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README.md
2.59 KB
Abstract
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.
README: Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation
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 contains all reactant structures used in the calculations, as denoted by
_r_in the file name. - Files beginning with
mX0have X = 0a oxy-functionalization (DKE 1) or site-specific oxy-functionalization within X = 1, 2, 3, or 4 conjoining bonds of the nitrogen (DKE 2–5, respectively). - Files beginning with
m0Xhave X = 0b oxy-functionalization (DKE 6) or site-specific oxy-functionalization within X = 1, 2, or 3 conjoining bonds of the triketone (DKE 7–9, respectively). - The final number in the file name differentiates the conformers of the molecule.
- For example,
m10_r_10.xyzis the 10th conformer of the reactant of DKE 2, with oxy-functionalization within 1 conjoining bond of the nitrogen.
- This directory contains all reactant structures used in the calculations, as denoted by
./transition_states- This directory contains all transition state structures used in the calculations, as denoted by
_ts_in the file name. - Files beginning with
mX0have X = 0a oxy-functionalization (DKE 1) or site-specific oxy-functionalization within X = 1, 2, 3, or 4 conjoining bonds of the nitrogen (DKE 2–5, respectively). - Files beginning with
m0Xhave X = 0b oxy-functionalization (DKE 6) or site-specific oxy-functionalization within X = 1, 2, or 3 conjoining bonds of the triketone (DKE 7–9, respectively). - The final number in the file name differentiates the conformers of the molecule.
- For example,
m10_ts_10.xyzis the 10th conformer of the transition state of DKE 2, with oxy-functionalization within 1 conjoining bond of the nitrogen.
- This directory contains all transition state structures used in the calculations, as denoted by