Dangling-End Double Networks: Tapping Hidden Toughness in Highly Swollen Thermoplastic Elastomer Hydrogels

This report introduces a unique method of significantly improving toughness in highly swollen block copolymer-based thermoplastic elastomer (TPE) hydrogels by converting an intrinsically large population of dangling chain ends into a mechanically active second network. In one form, the TPE hydrogels developed by our group are based on swelling of a vitrified melt-blend of two amphiphilic block copolymer species, sphere-forming polystyrene-poly­(ethylene oxide) (SO-H) diblock and triblock (SOS) copolymers. Here, the PEO midblock in the SOS triblock copolymer serves to tether adjacent PS spherical aggregates, producing hydrogel networks that are incredibly elastic and mechanically robust, preserving their shape even at the very high intrinsic swelling ratios produced at low SOS concentrations (e.g, 37 g of H₂O/(g of polymer) at 3.3 mol % SOS). In this report, we advance the utility of this framework by exploiting the hundreds of dangling PEO chain ends per spherical aggregate to form a second, mechanically active network. The approach is based on a stepwise installation of two tethering SOS triblock copolymer populations. The first is present directly during <i>melt-state</i> self-assembly of the original diblock/triblock copolymer blend and inherently determines the equilibrium swelling ratio of resulting hydrogel. The second population is then introduced <i>postswelling</i>, by simply coupling the dangling SO diblock copolymer chain ends under conditions largely free of the mechanical stress osmotically imposed on the primary network. Notably, this action simply shifts the ratio of diblock and triblock copolymer without compromising the thermoplasticity of the network. Here, we use the facile water-based coupling of PEO-terminal azide and alkyne groups to demonstrate the scale of toughness enhancements possible through conversion of dangling ends into a second network. The dangling-end double networks produced exhibit remarkable improvements in tensile properties (tensile modulus, toughness, strain at break, and stress at break), including a 58-fold increase in mean toughness (to 361 kJ/m³) and a 19-fold increase in mean stress to break (to 169 kPa) in highly swollen samples containing up to 95% (g/g) water. Importantly, these improvements could be realized without altering water content, shape, small-strain dynamic shear, and unconfined compressive properties of the original TPE hydrogels

The Role of Architecture in the Melt-State Self-Assembly of (Polystyrene)_star-<i>b</i>‑(Polyisoprene)_linear-<i>b</i>‑(Polystyrene)_star Pom-Pom Triblock Copolymers

Using a unique one-pot convergent anionic polymerization strategy, 18 (polystyrene)_star-<i>b</i>-(polyisoprene)_linear-<i>b</i>-(polystyrene)_star (S_<i>n</i>IS_<i>n</i>) pom-pom triblock copolymers were synthesized varying a range of architectural parameters including PS arm molecular weight (<i>M</i>_n,star), the number of arms contained in the star (<i>n</i>), and the PI midblock molecular weight (<i>M</i>_n,PI). A selected series of five of these 18, in which <i>M</i>_n,star was held approximately constant between 14.3 and 16.5 kDa, but with the numbers of arms in the star and PI midblock molecular weight varied, were selected for detailed characterization using rheology, AFM, and SAXS. The five selected all shared PS as the minority component, with star volume fractions (<i>f</i>_PS) varying between 0.11 and 0.22. All samples showed clear phase separation, with three of the five adopting a highly ordered hexagonal packing of cylinders (HPC) confirmed through SAXS and AFM. The remaining two systems were limited to liquid-like packing of cylindrical domains (LLP). Longer midblock molecular weights and increased numbers of arms in the star both showed a propensity to hinder formation of a highly ordered hexagonal lattice. Increasing the number of arms in the star also favored transitions to a disordered phase at lower temperatures when overall S_<i>n</i>IS_<i>n</i> molecular weight was held constant. The behavioral trends identified suggest interfacial packing frustration plays a prominent role in determining the ability of the system to develop highly ordered periodic structures. The chain crowding produced by the PS star architecture intrinsically favors interfacial curvature toward the majority PI component, contrary to that intrinsically favored by the block composition alone. In the two systems in which the frustration was architecturally most severe (largest <i>n</i> of 7.1, highest <i>M</i>_n,PI of 191 kDa), evolution of a hexagonal lattice could not be induced, even after significant thermal annealing. The pom-pom architecture itself also appears to have a significant impact on entanglement relaxation dynamics, with development of HPC morphologies only possible at elevated temperatures

Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts

The development of nanostructured polymeric systems containing directionally continuous poly­(ionic liquid) (poly­(IL)) domains has considerable implications toward a range of transport-dependent, energy-based technology applications. The controlled, synthetic integration of poly­(IL)­s into block copolymer (BCP) architectures provides a promising means to this end, based on their inherent ability to self-assemble into a range of defined, periodic morphologies. In this work, we report the melt-state phase behavior of an imidazolium-containing alkyl–ionic BCP system, derived from the sequential ring-opening metathesis polymerization (ROMP) of imidazolium- and alkyl-substituted norbornene monomer derivatives. A series of 16 BCP samples were synthesized, varying both the relative volume fraction of the poly­(norbornene dodecyl ester) block (<i>f</i>_DOD = 0.42–0.96) and the overall molecular weights of the block copolymers (<i>M</i>_n values from 5000–20 100 g mol^–1). Through a combination of small-angle X-ray scattering (SAXS) and dynamic rheology, we were able to delineate clear compositional phase boundaries for each of the classic BCP phases, including lamellae (Lam), hexagonally packed cylinders (Hex), and spheres on a body-centered-cubic lattice (S_BCC). Additionally, a liquid-like packing (LLP) of spheres was found for samples located in the extreme asymmetric region of the phase diagram, and a persistent coexistence of Lam and Hex domains was found in lieu of the bicontinuous cubic gyroid phase for samples located at the intersection of Hex and Lam regions. Thermal disordering was opposed even in very low molecular weight samples, detected only when the composition was highly asymmetric (<i>f</i>_DOD = 0.96). Annealing experiments on samples exhibiting Lam and Hex coexistence revealed the presence of extremely slow transition kinetics, ultimately selective for one or the other but not the more complex gyroid phase. In fact, no evidence of the bicontinuous network was detected over a 2 month annealing period. The ramifications of these results for transport-dependent applications targeting the use of highly segregated poly­(IL)-containing BCP systems are carefully considered

Network Formation in an Orthogonally Self-Assembling System

Many supramolecular motifs self-assemble into nanorods, forming the basis of the mechanical properties of supramolecular polymers. When integrated as end-caps in a bifunctional telechelic polymer, the motifs can phase segregate into the same or into another nanorod. In the latter case, a functional cross-link is formed by the bridging chain that strengthens the polymer network. This study introduces a supramolecular polymeric system that consists of two different nanorod forming supramolecular motifs. When end-capped to monofunctional polymers, these supramolecular motifs self-assemble in an orthogonal fashion in two separate types of noncross-linked nanorods, resulting in a viscous liquid lacking macroscopic properties. The addition of 15 mol % of an α,ω-telechelic polymer containing both supramolecular motifs, each on one end, transforms this viscous sticky liquid to a solid material with elastomeric properties due to network formation between the two types of nanorods