Tuning Hydrogel Mechanics by Kinetically Dependent Cross-Linking
2019
Free radical polymerization is an extensively used method to form a hydrogel network, in which the spatial inhomogeneity can be manipulated by kinetic control. However, it is still a challenge to direct mechanical properties by tuning the kinetics of free radical polymerization. Herein, kinetically dependent cross-linking is used to directly connect with the mechanical properties of hydrogels by tuning the reactivity of the macro-cross-linkers. F127 (PEO99–PPO65–PEO99) diallyl ether (F127DE) macro-cross-linker with low reactivity was first synthesized, and it can induce inner-micelles cross-linking due to its kinetic characteristic that its incorporation in the primary chain is slow at an early stage while rapid at a late stage of copolymerization with acrylamide (AAm) monomer. Thus, the highly cross-linked agglomerations can be effectively controlled in the well-dispersed micelle cross-linking, leading to an internally cross-linked micelle that is far stronger than a micelle formed only by weak supramole...
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