Colloidal Encapsulation of Hydrolytically and Oxidatively Unstable Organoborane Catalysts and Their Use in Waterborne Acrylic Polymerization

Trialkylborane catalysts and their amine complexes are hydrolytically and oxidatively unstable, decomposing in water very rapidly to trialkylboroxin, borate esters, and boric acid. However, trialkylborane−amine complexes will rapidly partition to a colloidal phase and remain surprisingly stable for long periods of time (>3 months) until such time as the catalyst is brought into an environment convenient for phase transfer. We show that tributylborane−amine complexes can be stored in aqueous solutions of several water-miscible polymers. We show by diffusion-oriented spectroscopy (DOSY) NMR experiments that the tributylborane−amine catalyst diffuses at nearly the same rate as the colloidal phase, providing strong evidence that they coexist. The aqueous colloidal catalysts can then be mixed with polymerizable monomers such as acrylates to produce good-quality polymers. We show that these colloid-encapsulated catalysts are also useful in producing adhesives capable of adhering low-surface-energy plastic substrates, even when formulated in systems containing 45% water. This is the first report of a waterborne structural adhesive.