Controlled Synthesis of Statistical Polycarbonates Based on Epoxides and CO₂

The controlled synthesis of terpolymer structures is often limited by the intrinsic reactivities of the monomers. For the synthesis of a statistical terpolymer from cyclohexene oxide (CHO) and propylene oxide (PO) with CO₂, an instrumental solution is demanded. Implementing a setup where one monomer can be added to the reaction mixture over the whole course of the reaction, the random distribution of the epoxides over the whole chain is realized. The successful terpolymerization can be determined with diffusion‐ordered nuclear magnetic resonance spectroscopy and gel permeation chromatography measurements while the statistical microstructure of the generated polymers is indicated in NMR spectroscopy and differential scanning calorimetry measurements. Furthermore, the concept is transferred to the terpolymerization of limonene oxide with PO and CO₂ underlining the versatility of the setup.