Bio-based polycarbonate as synthetic toolbox

Abstract

Completely bio-based poly(limonene carbonate) is a thermoplastic polymer, which can be synthesized by copolymerization of limonene oxide (derived from limonene, which is found in orange peel) and CO2. Poly(limonene carbonate) has one double bond per repeating unit that can be exploited for further chemical modifications. These chemical modifications allow the tuning of the properties of the aliphatic polycarbonate in nearly any direction. Here we show synthetic routes to demonstrate that poly(limonene carbonate) is the perfect green platform polymer, from which many functional materials can be derived. The relevant examples presented in this study are the transformation from an engineering thermoplastic into a rubber, addition of permanent antibacterial activity, hydrophilization and even pH-dependent water solubility of the polycarbonate. Finally, we show a synthetic route to yield the completely saturated counterpart that exhibits improved heat processability due to lower reactivity.

Acid-Labile Surfactants Based on Poly(ethylene glycol), Carbon Dioxide and Propylene Oxide: Miniemulsion Polymerization and Degradation Studies

“…In a comprehensive work of Hauenstein et al limonene based, water-soluble polycarbonates were investigated regarding their degradation in aqueous solution at different pH values. The lack of degradation observed in this work was explained by steric shielding due to the side chains [31]. Darensbourg and coworkers focused on the degradation of water-soluble polycarbonates in basic conditions using deprotonated carboxylic acid pendent groups as side chains [32].…”

Click Chemistry in Functional Aliphatic Polycarbonates

“…Besides ring‐opening polymerization of cyclic carbonate monomers, CO 2 ‐epoxy addition polymerization also plays an important role in the synthesis of functional aliphatic polycarbonates . For example, the copolymerization of limonene oxide and CO 2 gave a polycarbonate platform in which the double bond was used for thiol‐ene reaction to produce rubber, antibacterial polymer, heat processing grade material, and sea water soluble polymer, as shown in Figure . In the presence of dithiols, double‐bond‐containing polycarbonates were able to yield crosslinked polymers with improved thermal properties .…”

“…These post‐polymerization modifications provided a versatile approach to tune the properties of aliphatic polycarbonates. Reproduced with permission . Copyright 2016, Macmillan Publishers Limited, part of Springer Nature.…”

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

“…In this study, we focused on the catalytic transformation of the most abundant compounds, limonene preferentially, into the mono‐epoxides. Indeed, the limonene oxides can be used as platform molecules for the synthesis of multifunctional bio‐based polycarbonates polymers …”