Polymerization of methyl methacrylate by latent pre-catalysts based on CO2-protected N-heterocyclic carbenes

Abstract

Various carbon dioxide-protected N-heterocyclic carbenes (NHCs) have been investigated with regard to their ability to act as thermally latent initiators for the polymerization of methyl methacrylate (MMA). Such CO₂-protected NHCs, while completely inactive at room temperature, deliver poly(methyl methacrylate) (PMMA) in high yields upon heating and thus represent truly latent pre-catalysts. Polymerizations were conducted in the bulk, semi-bulk and in solution. Especially tetrahydropyrimidinium-2-carboxylates as well as 1,3-di(tert-butyl)imidazolium-2-carboxylate, both in combination with dimethylsulfoxide (DMSO), were identified as suitable pre-catalysts for the polymerization of MMA. With 1,3-di(tert-butyl)imidazolium-2-carboxylate in toluene, polydispersity indices (PDIs) as low as 1.3 and number-average molecular weights (M_n) of 500 000 g mol⁻¹ could be realized. Tetrahydropyrimidinium-2-carboxylates in conjunction with DMSO resulted in lower molecular weights. Notably, isolated polymer yields up to 96% were possible in some cases, though yields proved to be sensitive to the structure of the initiators used. In principle, at least two different polymerization mechanisms are active. In the presence of DMF or DMSO, the formation of a solvent anion (e.g., DMSO⁻), which then reacts with the monomer, is proposed. What follows is that only highly basic NHCs work well under these conditions. In contrast, the polymerization of MMA in toluene or in the bulk is probably governed by the nucleophilicity of the NHC, rendering unsaturated, less basic NHCs more applicable. Both mechanisms are discussed.