The zwitterionic organopolymerization of four different acrylic monomers (N,N-dimethylacrylamide, methyl acrylate, methyl methacrylate and tert-butyl methacrylate) based on neutral initiators, so-called N-heterocyclic olefins (NHOs), is presented. The scope and underlying (deactivation-)mechanisms were studied in a combined experimental and computational effort. From a range of differently structured NHOs it was shown that imidazole-derivatives, in contrast to imidazoline- and benzimidazole-derivatives, readily polymerize the selected monomers. While the additive-free reactions proceed with a relatively low degree of control to yield a largely atactic material, for the acrylamide the addition of LiCl as a Î¼-type ligand has been shown to result in a rapid and quantitative monomer consumption. The thus generated poly(N,N-dimethyl acrylamide) was found to be highly isotactic (>90% isotactic dyads) with high molecular weight (Mn= 250000-650000 g mol-1, DM= 1.3-1.6). Complementing DFT calculations considered the zwitterionic chain growth with respect to competing side reactions, namely spirocycles and enamine formation. It was found that NHOs with an unsaturated backbone better support the zwitterionic chain growth, with the spirocycles acting as dormant species that slow down but do not quench the polymerization process. Contrasting this, enamine formation irreversibly terminates the polymerization and is found to be energetically favored. This pathway can be blocked by the introduction of substituents on the exocyclic carbon of the NHO, resulting in structures like 2-isopropylidene-1,3,4,5-tetramethylimidazoline (4) which consequently deliver the most controlled polymerizations. Finally, a good correlation of the initiation energy barrier with the buried volume (%VBur) and the Parr electrophilicity index is described, allowing for a quick and reliable screening of potential monomers based on these two readily accessible parameters.
|Titolo:||N-Heterocyclic olefins as initiators for the polymerization of (meth)acrylic monomers: A combined experimental and theoretical approach|
|Data di pubblicazione:||2017|
|Appare nelle tipologie:||1.1.1 Articolo su rivista con DOI|