More Like this

1. Polyester networks from structurally similar monomers: recyclable-by-design and upcyclable to photopolymers

   https://doi.org/10.1039/D3PY00338H  

   Musgrave, Grant M.; Bishop, Katie M.; Kim, John S.; Heiner, Amelia C.; Wang, Chen (June 2023, Polymer Chemistry)

   Epoxy-based polymer networks from step-growth polymerizations are ubiquitous in coatings, adhesives, and as matrices in composite materials. Dynamic covalent bonds in the network allow its degradation into small molecules and thus, enable chemical recycling; however, such degradation often requires elevated temperatures and costly chemicals, resulting in various small molecules. Here, we design crosslinked polyesters from structurally similar epoxy and anhydride monomers derived from phthalic acid. We achieve selective degradation of the polyesters through transesterification reactions at near-ambient conditions using an alkali carbonate catalyst, resulting in a singular phthalic ester. We also demonstrate upcycling the network polyesters to photopolymers by one-step depolymerization using a functional alcohol. 

   more » « less
2. Mesoscale Modeling of Phase Separation Controlled by Hydrosilylation in Polyhydromethylsiloxane (PHMS)-Containing Blends

   https://doi.org/10.3390/nano12183117  

   Xiong, Yao; Choudhury, Chandan K.; Palkar, Vaibhav; Wunderlich, Raleigh; Bordia, Rajendra K.; Kuksenok, Olga (September 2022, Nanomaterials)

   Controlling morphology of polysiloxane blends crosslinked by the hydrosilylation reaction followed by pyrolysis constitutes a robust strategy to fabricate polymer-derived ceramics (PDCs) for a number of applications, from water purification to hydrogen storage. Herein, we introduce a dissipative particle dynamics (DPD) approach that captures the phase separation in binary and ternary polymer blends undergoing hydrosilylation. Linear polyhydromethylsiloxane (PHMS) chains are chosen as preceramic precursors and linear vinyl-terminated polydimethylsiloxane (v-PDMS) chains constitute the reactive sacrificial component. Hydrosilylation of carbon–carbon unsaturated double bonds results in the formation of carbon–silicon bonds and is widely utilized in the synthesis of organosilicons. We characterize the dynamics of binary PHMS/v-PDMS blends undergoing hydrosilylation and ternary blends in which a fraction of the reactive sacrificial component (v-PDMS) is replaced with the non-reactive sacrificial component (methyl-terminated PDMS (m-PDMS), polyacrylonitrile (PAN), or poly(methyl methacrylate) (PMMA)). Our results clearly demonstrate that the morphology of the sacrificial domains in the nanostructured polymer network formed can be tailored by tunning the composition, chemical nature, and the degree of polymerization of the sacrificial component. We also show that the addition of a non-reactive sacrificial component introduces facile means to control the self-assembly and morphology of these nanostructured materials by varying the fraction, degree of polymerization, or the chemical nature of this component. 

   more » « less
3. Fluid separation and network deformation in wetting of soft and swollen surfaces

   https://doi.org/10.1038/s43246-021-00125-2  

   Cai, Zhuoyun; Skabeev, Artem; Morozova, Svetlana; Pham, Jonathan_T (February 2021, Communications Materials)

   Abstract When a water drop is placed onto a soft polymer network, a wetting ridge develops at the drop periphery. The height of this wetting ridge is typically governed by the drop surface tension balanced by elastic restoring forces of the polymer network. However, the situation is more complex when the network is swollen with fluid, because the fluid may separate from the network at the contact line. Here we study the fluid separation and network deformation at the contact line of a soft polydimethylsiloxane (PDMS) network, swollen with silicone oil. By controlling both the degrees of crosslinking and swelling, we find that more fluid separates from the network with increasing swelling. Above a certain swelling, network deformation decreases while fluid separation increases, demonstrating synergy between network deformation and fluid separation. When the PDMS network is swollen with a fluid having a negative spreading parameter, such as hexadecane, no fluid separation is observed. A simple balance of interfacial, elastic, and mixing energies can describe this fluid separation behavior. Our results reveal that a swelling fluid, commonly found in soft networks, plays a critical role in a wetting ridge. 

   more » « less
4. A design framework for actively crosslinked filament networks

   https://doi.org/10.1088/1367-2630/abd2e4  

   Fürthauer, Sebastian; Needleman, Daniel J.; Shelley, Michael J. (January 2021, New Journal of Physics)

   Abstract Living matter moves, deforms, and organizes itself. In cells this is made possible by networks of polymer filaments and crosslinking molecules that connect filaments to each other and that act as motors to do mechanical work on the network. For the case of highly cross-linked filament networks, we discuss how the material properties of assemblies emerge from the forces exerted by microscopic agents. First, we introduce a phenomenological model that characterizes the forces that crosslink populations exert between filaments. Second, we derive a theory that predicts the material properties of highly crosslinked filament networks, given the crosslinks present. Third, we discuss which properties of crosslinks set the material properties and behavior of highly crosslinked cytoskeletal networks. The work presented here, will enable the better understanding of cytoskeletal mechanics and its molecular underpinnings. This theory is also a first step toward a theory of how molecular perturbations impact cytoskeletal organization, and provides a framework for designing cytoskeletal networks with desirable properties in the lab. 

   more » « less
5. Sequence and gelation in supramolecular polymers

   https://doi.org/10.1063/5.0218748  

   Balzer, Christopher; Fredrickson, Glenn H (August 2024, The Journal of Chemical Physics)

   Supramolecular polymer networks exhibit unique and tunable thermodynamic and dynamic properties that are attractive for a wide array of applications, such as adhesives, rheology modifiers, and compatibilizers. Coherent states (CS) field theories have emerged as a powerful approach for describing the possibly infinite reaction products that result from associating polymers. Up to this point, CS theories have focused on relatively simple polymer architectures. In this work, we develop an extension of the CS framework to study polymers with reversible bonds distributed along the polymer backbone, opening a broad array of new materials that can be studied with theoretical methods. We use this framework to discern the role of reactive site placement on sol–gel phase behavior, including the prediction of a microstructured gel phase that has not been reported for neutral polymer gels. Our results highlight the subtleties of thermodynamics in supramolecular polymers and the necessity for theories that capture them. 

   more » « less