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Rylski, Adrian K.

Publications and source records attributed to Rylski, Adrian K..

Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene-based ABA triblock copolymers, this gap is filled. Ring-opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin-like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high-performance plastics (≈260 °C). Here, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next-generation TPEs that are both biologically soft yet thermomechanically durable.

36 MATERIALS SCIENCE↗

Multimorphic Materials: Spatially Tailoring Mechanical Properties via Selective Initiation of Interpenetrating Polymer Networks

Access to multimaterial polymers with spatially localized properties and robust interfaces is anticipated to enable new capabilities in soft robotics, such as smooth actuation for advanced medical and manufacturing technologies. Here, orthogonal initiation is used to create interpenetrating polymer networks (IPNs) with spatial control over morphology and mechanical properties. Base catalyzes the formation of a stiff and strong polyurethane, while blue LEDs initiate the formation of a soft and elastic polyacrylate. IPN morphology is controlled by when the LED is turned “on”, with large phase separation occurring for short time delays (≈1–2 min) and a mixed morphology for longer time delays (>5 min), which is supported by dynamic mechanical analysis, small angle X-ray scattering, and atomic force microscopy. Through tailoring morphology, tensile moduli and fracture toughness can be tuned across ≈1–2 orders of magnitude. Furthermore, a simple spring model is used to explain the observed mechanical behavior. Photopatterning produces “multimorphic” materials, where morphology is spatially localized with fine precision (<100 µm), while maintaining a uniform chemical composition throughout to mitigate interfacial failure. As a final demonstration, the fabrication of hinges represents a possible use case for multimorphic materials in soft robotics.

36 MATERIALS SCIENCE↗

Polymeric multimaterials by photochemical patterning of crystallinity

An organized combination of stiff and elastic domains within a single material can synergistically tailor bulk mechanical properties. However, synthetic methods to achieve such sophisticated architectures remain elusive. We report a rapid, facile, and environmentally benign method to pattern strong and stiff semicrystalline phases within soft and elastic matrices using stereo-controlled ring-opening metathesis polymerization of an industrial monomer, cis -cyclooctene. Dual polymerization catalysis dictates polyolefin backbone chemistry, which enables patterning of compositionally uniform materials with seamless stiff and elastic interfaces. Visible light–induced activation of a metathesis catalyst results in the formation of semicrystalline trans polyoctenamer rubber, outcompeting the formation of cis polyoctenamer rubber, which occurs at room temperature. This bottom-up approach provides a method for manufacturing polymeric materials with promising applications in soft optoelectronics and robotics.

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