A simplified approach for the metal-free polymerization of propylene oxide.

Triethyl borane (EtB), in combination with phosphazene-type superbases, has recently emerged as a powerful co-catalyst for the anionic polymerization of epoxides. Here, it is demonstrated that the monomer-activating property of EtB can also compensate for the application of much gentler organobases. This not only results in simpler setups, but also significantly reduces nucleophilicity/basicity-derived side reactions. Notably, this principle applies to such a degree that simple 4-dimethylaminopyridine (DMAP) or 1,4-diazabicyclo[2.2.2]octane (DABCO) can serve to polymerize propylene oxide (PO). With suitable initiators, this results for example in very well-defined block copolyethers ( ≤ 1.03) without requiring work-up to remove side products such as PPO homopolymer. Performance correlates nicely with the corresponding organobase proton affinities (PAs), and a limiting PA of 220-230 kcal mol was identified for successful PO polymerization.