A Systematic Study of Nonionic Di‐ and Multiborane Catalysts for the Oligomerization and Polymerization of Epoxides

Borane catalysis has emerged as a powerful technology in epoxide polymerization. Still, the structure-activity correlations for these catalysts are not fully understood to date, especially regarding compounds with nonionic backbones. Thus, in this work, 13 different borane catalysts of this respective type are described and investigated for their epoxide oligomerization and polymerization performance, using propylene oxide (PO), 1-butylene oxide (BO) and allyl glycidyl ether (AGE) as monomers. Structurally, special emphasis is put on catalysts with different linker lengths and linker flexibilities as well as the introduction of more than two borane functionalities. Importantly, this screening is conducted both under typical polymerization conditions as well as under the chain transfer agent (CTA)-rich conditions relevant for large-scale production. It is found that suitable preorganization of the borane groups, such as present in biphenyl derivatives, offers a simple route to high-performing catalysts and quantitative monomer conversion of the investigated epoxides. Furthermore, it is demonstrated that a diborane-catalyzed oligomerization can be kept active over weeks, whereby repeated addition of monomer batches (14 steps) constantly results in full conversion and well-defined oligoethers, underlining the practical potential of this method. The absence of co-initiating counter ions is suggested as an inherent advantage of nonionic catalysts.