Ring-Opening Polymerization of Trimethylene Carbonate Catalyzed by Methanesulfonic Acid: Activated Monomer versus Active Chain End Mechanisms

The ring-opening polymerization (ROP) of trimethylene carbonate (TMC) initiated by water or n-pentanol and catalyzed by trifluoromethanesulfonic acid (HOTf) or methanesulfonic acid (MSA) has been investigated. In contrast with HOTf, MSA was found to afford poly(trimethylene carbonate) (PTMC) free of ether linkages even under forcing conditions. The comparison of the two acids substantiates further that activity does not simply correlate with acidity. Analysis of the resulting PTMC by Size Exclusion Chromatography (SEC), 1H NMR spectroscopy and mass spectrometry revealed the absence of molar mass control due to the formation of two polymer populations. This phenomenon was unambiguously attributed to the occurrence of two competitive mechanisms, namely Activated Monomer (AM) and Active Chain End (ACE). Such a situation is frequently encountered in the ROP of cyclic ethers, but is unprecedented for cyclic carbonates. Its deleterious impact on the polymerization control can be significantly reduced by maintaining the monomer concentration low enough so as to minimize the ACE mechanism. Accordingly, multifeed or continuous addition of the carbonate was shown to impart good control of molar mass and end-group fidelity.