Shape memory hydrogels have promising applications in a wide variety of fields. Here we report the facile fabrication of a novel type of shape memory hydrogels physically cross-linked with both stronger and weaker hydrogen bonding (H-bonding). Strong multiple H-bonding formed between poly(vinyl alcohol) (PVA) and tannic acid (TA) leads to their coagulation when they are physically mixed at an elevated temperature and easy gelation at room temperature. The amorphous structure and strong H-bonding endow the PVA-TA hydrogels with excellent mechanical properties, as indicated by their high tensile strengths (up to 2.88 MPa) and high elongations (up to 1100%). The stronger H-bonding between PVA and TA functions as the "permanent" cross-link and the weaker H-bonding between PVA chains as the "temporary" cross-link. The reversible breakage and formation of the weaker H-bonding imparts the PVA-TA hydrogels with excellent temperature-responsive shape memory. Wet and dried hydrogel samples with a deformed or elongated shape can recover to their original shapes when immersed in 60 °C water in a few seconds or at 125 °C in about 2.5 min, respectively.
Graphene oxide (GO) is effective in catalyzing a wide variety of organic reactions and a few types of polymerization reactions. No radical chain polymerizations catalyzed by GO have been reported. In this article, we probe the catalytic role and acceleration effect of GO for self-initiated radical chain polymerizations of acrylic acid (AA) in the presence of GO and a pre-existing polymer, poly(N-vinylpyrrolidone) (PVP), from a calorimetric perspective. Gelation experiments and DSC studies show that GO can function as a catalyst to accelerate the radical chain polymerization of AA. Isothermal polymerization kinetic data shows that the addition of GO diminishes the induction periods and increases the polymerization rates, as indicated by the much enhanced overall kinetic rate constants and lowered activation energies. The catalytic effect of GO for the polymerization of AA is attributed to the acidity of GO and the hydrogen bonding interactions between GO and monomer molecules and/or polymers.
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