LAUSR

The N-heterocyclic carbene 1,3-di-tert-butylimidazol-2-ylidene (NHCtBu) and its 1:1 adduct with methyl sorbate (MS) were found to initiate anionic polymerization of N-substituted maleimides (RMIs) in organic solvents at −20 °C to afford linear and cyclic poly(RMI)s, respectively. Quantitative monomer consumption was observed when a bulky aluminum Lewis acid, such as methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD), was used as an additive. In the presence of the NHCtBu:MS adduct as an initiator, monomer consumption was followed by ring closure without the need for highly diluted conditions to give cyclic poly(RMI)s containing α-terminal MS units, which exhibited an Mn of 3.4 × 103–6.2 × 103 and a broad polydispersity index (Mw/Mn = 2.43–2.65). Dilution was not required due to the presence of an α-terminal NHCtBu group, which acted as a counter cation for the propagating center during polymerization. The broad molecular weight distributions of the obtained polymers were ascribed to a chain transfer upon abstraction of the α-carbonyl proton of the RMIs, particularly to the neighboring NHCtBu cation unit. 1H NMR and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass analyses indicated that the proton transfer of the acidic proton was induced by the propagating anion. The topologies of the linear and cyclic poly(RMI)s were directly observed by transmission electron microscopy (TEM). Direct Observation of Cyclic Poly(N-substituted maleimide)s with Broad Size Distributions Synthesized by Anionic Polymerization using an N-Heterocyclic Carbene and Successive Ring Closure Without High Dilutions.