Thermodynamics of the Carbon Dioxide–Epoxide Copolymerization and Kinetics of the Metal-Free Degradation: A Computational Study

Abstract

The copolymerization reactions of carbon dioxide and epoxides to give polycarbonates were examined by density functional theory (DFT), and chemically accurate thermochemical data (benchmarked to experimental values) were obtained via composite ab initio methods. All of the examples studied, i.e., formation of poly(ethylene carbonate), poly(propylene carbonate), poly(chloropropylene carbonate), poly(styrene carbonate), poly(cyclohexene carbonate), and poly(indene carbonate), exhibited enthalpies of polymerization of 21–23 kcal/mol, with the exception of poly(cyclopentene carbonate) (15.8 kcal/mol) which suffers both ring strain and intramolecular steric repulsion caused by the cyclopentane ring fused to the polymer chain. The metal-free carbonate backbiting reaction by a free anionic polycarbonate strand is inhibited by bulky groups at the methine carbon but is accelerated by resonance stabilization of the pentavalent transition state in the case involving poly(styrene carbonate). Nucleophilic attack at the methylene carbon of a substituted epoxide has a lower barrier than for the corresponding reaction involving ethylene oxide due to charges being distributed onto the pendant groups. The undesired backbiting reaction to afford cyclic organic carbonates observed under polymerization conditions for many systems due to the low activation barrier (ΔG‡ = 18–25 kcal/mol) was negligible for poly(cyclohexene carbonate) because, in this instance, it must overcome an additional endergonic conformational change (ΔG = 4.7 kcal/mol) before traversing the activation barrier (ΔG‡ = 21.1 kcal/mol) to cyclization. Backbiting from an alkoxide chain end is proposed to proceed via a tetrahedral alkoxide intermediate, where formation of this intermediate is barrierless. Further reaction of this intermediate to the cyclic carbonate has a free energy barrier 10 kcal/mol less than the carbonate chain end backbiting reaction.