Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters

Abstract

The synthesis of polymeric materials starting from CO2 as a feedstock is an active task of research. In particular, the copolymerization of CO2 with epoxides via ring-opening copolymerization (ROCOP) offers a simple, efficient route to synthesize aliphatic polycarbonates (APC). In many cases, APC display poor physical and chemical properties, limiting their range of application. The terpolymerization of CO2 with epoxides and organic anhydrides or cyclic esters offers the possibility, combining the ROCOP with ring-opening polymerization (ROP), to access a wide range of materials containing polycarbonate and polyester segments along the polymer chain, showing enhanced properties with respect to the simple APC. This review will cover the last advancements in the field, evidencing the crucial role of the catalytic system in determining the microstructural features of the final polymer.

One-pot terpolymerization of CHO, CO2andl-lactide using chloride indium catalysts

“…A wide range of different metal complexes has been reported for the development of biodegradable polycarbonates, polyesters and terpolymers. 6,14,26,27 Amongst them, it is worth highlighting the bimetallic zinc/magnesium β-diiminate (BDI) complexes, firstly described by Coates and co-workers. 28,29 They were found to be very efficient for the stereoselective ROP of lactide, affording the formation of isotactic, heterotactic and syndiotactic PLA from l -, rac - and meso -lactide respectively.…”

Metal Catalyzed Polymerization: From Stereoregular Poly(α‐olefins) to Tailor‐Made Biodegradable/Biorenewable Polymers and Copolymers

“…The large potentiality of ROCOP of epoxides with CO 2 or anhydrides has been also expressed in the possibility to combine the two catalytic processes with each other and/or with the ROP of lactones in switching catalysis strategies to produce block polymers by one pot procedures. [157,158] Among the catalytic systems able to promote ROCOP reactions in controlled manner, the most significant examples are salen complexes of trivalent metals such as Al(III), Cr(III) and Co(III) and complexes of bivalent metals such as Zn (II) and Mg(II) with nitrogen-or oxygen-based ligands. [156] Generally, they are used in combination with neutral or ionic nucleophilic species as cocatalysts for the formation of binary catalyst/ cocatalyst pairs.…”

“…First, these are 100 % atom efficient reactions, a crucial aspect to save materials and reduce waste production; moreover, the properties of the resulting materials can be easily manipulated by changing the structure of the epoxide, through reactions which generally proceed under similar conditions. The large potentiality of ROCOP of epoxides with CO 2 or anhydrides has been also expressed in the possibility to combine the two catalytic processes with each other and/or with the ROP of lactones in switching catalysis strategies to produce block polymers by one pot procedures [157,158] …”

Dinuclear chromium complexes with [OSSO]-type ligands in the copolymerization of epoxides with CO2and phthalic anhydride

“…More recently, attention has shifted to the terpolymerization of epoxides with CO 2 and cyclic anhydrides for the possibility of obtaining block copolymers with polycarbonate and polyester segments having different microstructural features and therefore offering a wider range of chemical and physical properties. 19–21…”