Journal
RSC ADVANCES
Volume 10, Issue 71, Pages 43389-43393Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0ra08970b
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- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) [358283783 - SFB 1333]
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Triethyl borane (Et3B), 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 Et3B 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 ((M) <= 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(-1) was identified for successful PO polymerization.
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