# Sustainable Polyaddition Path to Polyesters via Catalytic Homocoupling of Renewable Dicrotonate Monomers

## TL;DR

This paper introduces a sustainable method to create polyesters using renewable dicrotonate monomers and a simple catalyst, resulting in tunable, degradable materials.

## Contribution

A new catalytic polyaddition method for synthesizing alkene-functionalized polyesters from renewable dicrotonates is presented.

## Key findings

- Potassium tert-butoxide enables rapid polyester synthesis at room temperature with >99% conversion.
- Polyester properties can be adjusted by varying the bridging diol used in the reaction.
- The resulting materials are soft, amorphous, and degradable by hydrolysis.

## Abstract

The development of biorenewable polyhydroxyalkanoate
(PHA) chemistry
has generated interest in crotonate-based monomers as versatile building
blocks. Crotonates can be obtained through the pyrolysis of PHAs,
offering both a sustainable end-of-life pathway for PHAs and a renewable
route to crotonate monomers. This study presents a new polyaddition-type
step-growth polymerization of dicrotonates in which alkene-functionalized
polyesters are synthesized using potassium tert-butoxide
as a simple base catalyst. The reaction proceeds rapidly at room temperature,
achieving >99% conversion within seconds and requiring no byproduct
removal. The properties of the resulting polyesters can be tuned via
the choice of bridging diol, and the materials are degradable by hydrolysis.
The polymers reported herein are soft, amorphous solids with predominantly
cyclic architectures under standard conditions, while linear analogs
can be accessed through a chain-end-capping strategy. The work presented
herein bridges key principles of polymer sustainabilityincluding
biorenewability of feedstocks, energy-efficient synthesis, and degradable
end-of-life pathwayswith practical considerations essential
for real-world application, such as operational simplicity, scalability,
cost-effectiveness, and supply chain accessibility.