A versatile double-network (DN) hydrogel with two noncovalent crosslinked networks is synthesized by multiple hydrogen bonding (H-bonding) interactions. The DN hydrogels are synthesized via a heating-cooling photopolymerization process by adding all reactants of agar, N-acryloyl glycinamide (NAGA) and N-benzylacrylamide (NBAA) monomers, UV initiators to a single water pot. Poly(N-acryloyl glycinamide-co-N-benzyl acrylamide) (P(NAGA-co-NBAA)) with a triple amide in one side group is synthesized via UV-light polymerization between NAGA and NBAA, forming a strong intermolecular H-bonding network. Meanwhile, the intramolecular H-bonding network is formed between P(NAGA-co-NBAA) and agars. The sol-gel phase transition of agars at 86 °C generates the molecular entanglement network. Such a double network enables the hydrogel high self-healing efficiency (about 95%), good shape memory ability, and high mechanical strength (1.1 MPa). Additionally, the DN hydrogel is completely crosslinked by multiple hydrogen bonds (H-bonds) and the physical crosslinking of agar without extra potential toxic chemical crosslinker. The DN hydrogels find extensive applications in the biomedical materials due to their excellent biocompatibility.

Medical fixing is one of the very important applications of the shape-memory polymer material, and the two important properties of the medical fixing material are that it perfectly fits the body during the fixing and easily detaches after being used. As the fixing and detachment are triggered by two independent stimuli in two opposite directions, it is necessary to develop multidirectional triple-shape-memory polymers. In this research, a series of polymer materials composed of trans-polyisoprene (TPI) and paraffin were prepared by melt blending and compression molding, and then the TPI was cross-linked by vulcanization. As a result of the large difference in the melting temperature and crystallization temperature between TPI and paraffin, the obtained polymer materials exhibit a triple-shape-memory behavior. According to the analysis of crystal behavior, microscopic morphology, and mechanical properties of the materials with different paraffin contents and TPI cross-linking density by differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, and dynamic mechanical thermal analysis, the shape-memory behavior of the obtained materials was tunable by the cross-linking density of TPI and the crystallization degree of TPI or paraffin. Compared with the traditional triple-shape-memory material, our samples are prepared in a more facile way and can recover at human body temperature (37 °C). Moreover, our TPI/paraffin material can realize more flexible multidirectional recovery, as well as can be reprogramed and used multiple times. To the best of our knowledge, there are few polymer materials reported, which can realize multidirectional recovery. These unique multidirectional and reprogramable properties will enable the application of this polymer material, especially in the medical fixing materials.

The shape memory thermoplastic polyurethane (TPU) generally exhibits a phase-separated structure, in which the hard segments form the hard domains via hydrogen bonds, and plays an important role in shape recovery. However, the physical interaction in the hard domains is always weak, resulting in a permanent deformation and thus decreasing the shape-recovery ability of TPU significantly. In this research, a new type of diol chain extender containing anthracene groups was synthesized, and the photoresponsive anthracene groups were incorporated into the hard segment of TPU. The stability in hard domains and recoverability could be tailored by different UV irradiation times via the photodimerization of anthracene groups, and the shape-recovery ratio and the shape-fixing ratio were still both above 93%, even when the strain reached 270%. More importantly, the shape-free reconfiguration is achieved through the dimerization of anthracene groups under UV irradiation, which achieved free construction of three-dimensional (3D) shapes without templates. Thus, the spontaneous shape change from two-dimensional (2D) to 3D was realized, in combination with melting transition, and the dedimerization of anthracene ensured the recyclability of polyurethane at T = 150 °C. This simple and facile strategy could be used to fabricate the recyclable and photoplasticity shape memory TPU with a high shape-fixing/recovery ratio at large deformation, and it would have a wider range of potential application in stents.

Based on the adhesive mechanism of mussels, we present a facile strategy to prepare nanocomposite polydopamine–poly­(N-acryloyl glycinamide)–graphene oxide (PDA–PNAGA–GO) hydrogels with lots of catechol groups in the matrix of hydrogel. The microfibril structure formed by PDA chains enables the hydrogels high stretchability (∼1500%) and toughness (6990 J/m2); the multiple hydrogen bonding interactions and π–π interactions among the PNAGA network and PDA chains also enable a hydrogel perfect self-healing performance. Moreover, GO in the hydrogel can absorb the near-infrared irradiation, resulting in the temperature difference between the surface and bottom area and then a bending deformation (with 40% of actuation degree) of the hydrogel. Besides, the GO can also make the hydrogels electrically conductive, and the self-healing efficiency (∼87% for the first healing) could also be calculated according to the retention rate of conductivity of hydrogel after being healed at 90 °C. The unique properties will enable the PDA–PNAGA–GO hydrogels to be widely used in the field of tissue engineering and soft actuators.

Silicone rubber is a kind of elastomer with excellent biocompatibility and good resistance to high and low temperature, and can be used as the matrix of smart materials in the...