Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation

Area of Science:

• Polymer Chemistry
• Materials Science
• Chemical Engineering

Background:

• Controlling polymer bond reactivity is crucial for functionalization and chemical recycling.
• Macromolecular chain conformation effects on polymer bond reactivity remain underexplored.
• Developing polymers for a circular economy requires understanding deconstruction pathways.

Purpose of the Study:

• To investigate how oxy-functionalization of condensation polymers influences their acidolysis rate.
• To elucidate the role of chain conformation and transition state energies in polymer deconstruction.
• To demonstrate the potential of modified polydiketoenamines for efficient chemical recycling.

Main Methods:

• Oxy-functionalization of polydiketoenamines at specific amine or triketone segments.
• Acidolysis reactions to depolymerize the functionalized polymers.
• Analysis of distortion and interaction energies in rate-limiting transition states.

Main Results:

• Oxy-functionalization increased acidolysis rates by over three orders of magnitude.
• Specific site functionalization effectively controlled polymer deconstruction rates.
• Linear polydiketoenamine architectures were efficiently deconstructed.

Conclusions:

• Oxy-functionalization is a powerful strategy to control polydiketoenamine reactivity for chemical recycling.
• This approach enables efficient deconstruction of polymers, supporting a circular manufacturing economy.
• Modified polydiketoenamines show promise as recyclable adhesives for various surfaces.