Applications of Fast, Facile, Radiation-Free Radical Polymerization Techniques Enabled by Room Temperature Alkylborane Chemistry.

Fast, robust, and scalable techniques for covalent materials assembly are shown to be enabled by variants of a simple mixing-induced free radical initiation scheme broadly termed room-temperature alkylborane (RTA) chemistry. Unique process versatility, speed of reaction, high conversion, and structural control at ambient conditions occur by exploiting air-stable alkylborane-amine complexes that rapidly initiate upon mixing with common amine-reactive decomplexing agents such as carboxylic acid compounds. Three diverse application examples are presented, illustrating facile ambient routes to covalent assembly varying in length scale: (1) copolymers with controllable pressure-sensitive adhesive properties, (2) hydrophilically modified silicone microparticles from heterophase reactions, and (3) UV-free inkjet printable materials suitable for thick-textured patterning and printing, all conducted in open air with no radiation or atmospheric control. These examples demonstrate that this simple "bucket chemistry" can create intriguing degrees of freedom for polymerization, cross-linking and covalent macromolecular assembly with controllable structure and properties, suggesting further opportunities for both fundamental mechanistic investigation and application to a range of old and new materials assembly problems across length scales.