Preparation of Well-Defined Propargyl-Terminated Tetra-Arm Poly(N-isopropylacrylamide)s and Their Click Hydrogels Crosslinked with β-cyclodextrin

As an important class of reversible deactivation radical polymerization (RDRP), reversible addition fragmentation chain transfer (RAFT) polymerization has attracted great attention attributed to its facile and flexible features to prepare well-defined polymers with different complex structures. In addition, the combination of RAFT with click chemistry provides more effective strategies to fabricate advanced functional materials. In this work, a series of temperature responsive tetra-arm telechelic poly(N-isopropylacrylamide)s (PNIPAs) with propargyl end groups were prepared for the first time through RAFT and subsequent aminolysis/Michael addition modification. The temperature sensitivities of their aqueous solutions were researched via turbidity measurement. It was found that the phase transition temperature of obtained PNIPAs increased with their molecular weights ascribed to their distinctions in the hydrophobic/hydrophilic balance. Subsequently, beta-cyclodextrin (beta-CD) functionalized with azide moieties was used to crosslink the prepared propargyl-terminated tetra-arm PNIPAs through click chemistry, fabricating corresponding hydrogels with thermoresponse. Similar to their precursors, the hydrogels demonstrated the same dependence of volume phase transition temperature (VPTT) on their molecular weights. In addition, the incorporation of beta-CD and the residual groups besides crosslinking may provide a platform for imparting additional functions such as inclusion and adsorption as well as further functionalization.