Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate

Abstract

The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2 ) catalyzed by a zinc β-diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg ) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain. Moreover, polycarbonates bearing pendent cyclic carbonates can be quantitatively prepared by CO2 insertion catalyzed by lithium bromide.

CO2-fixation into cyclic and polymeric carbonates: principles and applications

“…Examples include polycarbonates prepared from CO 2 and indene oxide (with a T g up to 138°C vs. ∼150°C for BPA-PC), 236,237 limonene oxide (T g of 130°C, improved pencil hardness (B vs. 8B) and higher transparency (94% vs. 89%) compared to BPA-PC) 234,238 and limonene dioxide (T g up to 135°C for unmodified CO 2 /limonene dioxide polycarbonates). 239 Although the T g of these CO 2based polycarbonates match that of BPA-PC, their impact behaviour was not studied, thereby not (yet) demonstrating their suitability as replacements for BPA-PC in rigid engineering plastic.…”

Ring‐Opening Copolymerization of Epoxides with Cyclic Anhydrides Promoted by Bimetallic and Monometallic Phenoxy–Imine Aluminum complexes

“…As an onfoodr esource, it represents ag reat opportunity for sustainable catalysis. Them onomer is used for copolymerization with CO 2 [27] and with anhydrides. [28] Additionally,b earing av inyl pendant group as extra functionality,( R)-limoneneo fferst he opportunity of postpolymerization modifications to functional polymers.…”

Polymerisation of a terpene-derived lactone: a bio-based alternative to ε-caprolactone

“…Recent work has focused on the preparation of epoxides or anhydrides from terpenes as a route to producing polycarbonates or polyesters. [36][37][38][39][40] In these reports the thermal properties of the polymer have been modified by the incorporation of a renewable aliphatic moiety. This research is generally focused on production of high T g materials, whereas the work reported herein also demonstrates their utility as drop in replacements for low T g polymers.…”