Search

Design of the polymer networks with tunable mechanical properties and multishape memory effects (multi-SMEs) is highly desired in the engineering applications. Herein, we report on the stereocomplexed and homochiral polyurethane (PU) elastomers with tunable multi-SMEs by cross-linking the triblock prepolymers bearing the poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) enantiomeric segments. The homochiral PU is nearly amorphous, yet the stereocomplexed PU becomes highly crystalline due to the stereocomplexation of enantiomeric segments. Moreover, the two distinct thermal (glass, melting) transitions of PLLA (or PDLA) segments in PUs are integrated to realize the thermally induced triple- and quadruple-SMEs. Control over the enantiomeric segmental ratios allows the feasible manipulation of crystallizability, mechanical and thermal properties, and multi-SMEs of PUs.

Stereocomplexation of complementary chiral blocks has been a feasible way to prepare thermoresponsive physical gels (or thermogels). Understanding the thermoresponsive phase behavior of stereocomplexable amphiphilic copolymers in water is essential to prepare thermogels with tunable physical properties. Herein, we use an enantiomeric mixture of the poly(D-lactic acid) (PDLA)/poly(ethylene glycol) (PEG) diblock copolymer and the poly(L-lactic acid) (PLLA)/PEG triblock copolymer as a stereocomplexable system and report a novel thermogel that exhibits unique gel–sol–gel multiple transitions upon heating. The thermally-induced phase transition of the PEG–PDLA/PLLA–PEG–PLLA thermogel was governed by the copolymer composition and the stereocomplexation of PLLA/PDLA segments. The molecular motion of PEG segments enhances during the gel–sol transition but slows down in the subsequent sol–gel transition. The gel–sol and sol–gel transitions that occurred at low and high temperatures are driven by the increased mobility of PEG segments and micelles and the promoted PLLA/PDLA stereocomplexation, respectively. PEG–PDLA/PLLA–PEG–PLLA gels can be used to capsulate and release a hydrophobic drug; the drug release rate increases as the content of hydrophilic blocks increases.

Physical hydrogels crosslinked by non-covalent interactions have attained increasing attention due to their good mechanical properties and processability. However, the use of feasible and controllable non-covalent interactions is highly essential for preparing such hydrogels. In this article, we report on stereocomplexed physical hydrogels prepared by simple casting and swelling of amphiphilic graft copolymers bearing a poly(acrylic acid) (PAA) backbone and poly(l-lactic acid) (PLLA) or poly(d-lactic acid) (PDLA) stereocomplexable side chains. The microstructure, swelling behavior, and mechanical and shape memory properties of the obtained hydrogels can be tuned by varying the copolymer composition and stereocomplex (SC) crystallization of PLLA/PDLA enantiomeric chains. The long PLLA or PDLA chains segregate to form hydrophobic, crystallized domains in water, serving as physical crosslinking junctions for hydrogels. SC crystallization between PLLA and PDLA further enhances the number density of physical crosslinkers of enantiomerically mixed hydrogels. The SC content increases as the PLLA/PDLA ratio approaches 1/1 in enantiomerically mixed hydrogels. The average distance between crosslinking junctions declines for the hydrogels with a high PLLA (or PDLA) mass fraction (MPLA) and SC content, due to the increased number density of physical crosslinkers. Accordingly, the tensile strength and the Young's modulus increase but the swelling ratio and the elongation-at-break of the hydrogels decrease with an increase in MPLA and SC content. The hydrogels exhibit shape memory behavior; the shape fixing ability is enhanced by the SC crystallization of PLLA/PDLA side chains in the hydrogels.

Stimuli-responsive shape-transforming hydrogels have shown great potential toward various engineering applications including soft robotics and microfluidics. Despite significant progress in designing hydrogels with ever more sophisticated shape-morphing behaviors, an ultimate goal yet to be fulfilled is programmable reversible shape transformation. It is reported here that transient structural anisotropy can be programmed into copolymer hydrogels of N-isopropylacrylamide and stearyl acrylate. Structural anisotropy arises from the deformed hydrophobic domains of the stearyl groups after thermomechanical programming, which serves as a template for the reversible globule-to-coil transition of the poly(N-isopropylacrylamide) chains. The structural anisotropy is transient and can be erased upon cooling. This allows repeated programming for reversible shape transformation, an unknown feature for the current hydrogels. The programmable reversible transformation is expected to greatly extend the technical scope for hydrogel-based devices.

Constructing dual or multiple noncovalent crosslinks is highly effective to improve the mechanical and stimuli-responsive properties of supramolecular physical hydrogels, due to the synergistic effects of different noncovalent bonds. Herein, a series of tough physical hydrogels are prepared by solution casting and subsequently swelling the films of poly(ureidopyrimidone methacrylate-co-stearyl acrylate-co-acrylic acid). The hydrophobic interactions between crystallizable alkyl chains and the quadruple hydrogen bonds between ureidopyrimidone (UPy) motifs serve as the dual crosslinks of hydrogels. Synergistic effects between the hydrophobic interactions and hydrogen bonds render the hydrogels excellent mechanical properties, with tensile breaking stress up to 4.6 MPa and breaking strain up to 680%. The UPy motifs promote the crystallization of alkyl chains and the hydrophobic alkyl chains also stabilize UPy-UPy hydrogen bonding. The resultant hydrogels are responsive to multiple external stimuli, such as temperature, pH, and ion; therefore, they show the thermal-induced dual and metal ion-induced triple shape memory behaviors.