Elastomeric polysiloxane nanocomposites with elongations of >5000% (more than 3× greater than any previously reported material) with excellent shape recovery are presented. Highly deformable materials are desirable for the fabrication of stretchable implants and microfluidic devices. No crosslinking or domain formation is observed by a variety of analytical techniques, suggesting that their elastomeric behavior is caused by polymer chain entanglements.

Increasingly precise control of polymer architectures generated by “Living” Anionic Ring-Opening Polymerization (Living AROP) is leading to a broad range of commercial advanced material applications, particularly in the area of siloxane macromers. While academic reports on such materials remain sparse, a significant portion of the global population interacts with them on a daily basis—in applications including medical devices, microelectronics, food packaging, synthetic leather, release coatings, and pigment dispersions. The primary driver of this increased utilization of siloxane macromers is their ability to incorporate the properties of silicones into organic structures in a balanced manner. Compared to organic polymers, the differentiating properties of silicones—low Tg, hydrophobicity, low surface energy, and high free molal space—logically lend themselves to applications in which low modulus, release, permeability to oxygen and moisture, and tactile interaction are desired. However, their mechanical, structural and processing properties have until recently precluded practical applications. This review presents applications of “Living” AROP derived polymers from the perspective of historical technology development. Applications in which products are produced on a commercial scale—defined as not only offered for sale, but sold on a recurrent basis—are emphasized. Hybrid polymers with intriguing nanoscale morphology and potential applications in photoresist, microcontact printing, biomimetic soft materials, and liquid crystals are also discussed. Previously unreported work by the authors is provided in the context of this review.

Contact lenses are one of the most successful biomaterials in history with a global market estimated to be worth over $17 billion in 2025. Silicone hydrogel contact lenses dominate the market and are complex biphasic biomaterials with several critical material properties needed for clinical use. Careful consideration of composition and chemistry is needed to identify formulations of lenses meeting all commercial standards with the potential for improved manufacturability, cost, and/or next generation use. Four silicone macromers were investigated in this work with varying symmetry of siloxane units and macromer structure, number of siloxane groups, branching, length, and concentration. Novel silicone hydrogel lenses were produced and evaluated for optical transmittance, elastic modulus, oxygen transmissibility, water content, and surface wettability. Several lenses met commercial standards and demonstrated an increase in oxygen permeability (Dk) and inverse relationship with elastic modulus and siloxane concentration, respectively. A hydrophobic/hydrophilic ratio below 1.4 was needed for a co-continuous water phase. Substitution of methoxypropyl groups for butyl groups increased hydrophobic microdomains leading to decreased optical quality and mechanical properties. Generally, fluorine-containing silicone macromers allowed for a wider range of successful compositions, and above a certain hydrophilic composition, the presence of trifluoropropyl groups resulted in improved solubility and optically clear lenses. Data also showed asymmetric siloxane macromers have potential to meet critical lens properties at lower overall siloxane content. New lens materials with wider composition ranges meeting all clinical lens properties is a significant challenge and may significantly expand the field.

A facile technique was developed for a long-term increase in silicone elastomer surface hydrophilicity, eliminating the need for post-cure surface treatment (e.g. oxygen plasma or surface grafting). Well-defined silicones (1-4 kDa) with a central vinyl functionality and discrete PEG2, PEG3 and tetrahydrofurfuryl (THF) pendant endgroups were synthesized, characterized and used as comonomers in addition-cure, platinum catalyzed 2-part silicone elastomer formulations. The modified silicone elastomers were optically clear and maintained the mechanical performance characteristic of this class of material with up to 20 wt.% comonomer in the 2-part formulation. Contact angle measurements of deionized water on the silicone elastomer surface showed improved wettability with comonomer content. The elastomer surface shifted from hydrophobic (contact angle ∼120°C) to hydrophilic (contact angle < 90°C) at ∼5 wt.% comonomer loadings for extended time frames (> 5 months). Coefficient of friction measurements of the modified silicone elastomers revealed an increase in surface lubricity with comonomer loadings.

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