Combining ATRP and FRP Gels: Soft Gluing of Polymeric Materials for the Fabrication of Stackable Gels

Stackable gels comprised of layers of dissimilar polymers were synthesized by combining conventional free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) using two approaches: (i) polymerization of a pre-gel solution containing a monomer and cross-linker introduced on top of a previously prepared gel, and (ii) simultaneous polymerization of two immiscible pre-gel solutions remaining in contact. All permutations of FRP and ATRP yielded single-piece, connected, amphiphilic gels regardless of the order of polymerization. Furthermore, multi-layer ATRP gels combining different polymers were synthesized with the FRP layer as a gluing agent. A 10-layer amphiphilic stackable gel combining n-butyl methacrylate (BMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA), and a 10-layer stackable gel combining BMA, DMAEMA and di(ethyleneglycol) methyl ether methacrylate (PEO2MA) were synthesized. This patching method, combining conventional FRP gels with ATRP ones, offers an efficient path to the formation of complex stackable gel architectures.