Alkylborane-Initiated Thiol-Ene Networks for the Synthesis of Thick and Highly Loaded Nanocomposites.

Thiol-ene nanocomposites were synthesized for the first time using an alkylborane-ligand initiator complex under bulk and ambient conditions without external light or thermal stimuli. Initiation was triggered by the in situ decomplexation of an air-stable trialkylborane-amine complex to liberate trialkylborane, which rapidly autoxidizes with atmospheric oxygen and generates free radicals to drive thiol-ene polymerization. This chemically activated mode of initiation uniquely affords thiol-ene nanocomposites with an unrivaled carbon nanotube (CNT) loading of 1.3 wt % and thicknesses of ∼6.7 mm by circumventing restrictions imposed by long pathlengths and light-impeding fillers during photoinitiation. Alkylborane initiation also exhibited advantageous polymerization rates, equivalent to photoinitiation, resulting in network formation and gelation within minutes. Systematic studies were conducted to evaluate comparable alkylborane- and photo-initiated nanocomposites under progressively higher loadings and larger specimen thicknesses, revealing an enhancement or better retainment of mechanical performance in alkylborane-initiated nanocomposites.