Applications of Hybrid Polymers Generated from Living Anionic Ring Opening Polymerization

Abstract

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.

Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers: History and Prospects

“…The protecting group on PDMS was quantitatively removed by hydrogenolysis to give a secondary amine (Figure 14): A recent review by Goff J., Sulaiman S., and Arkles B. [98] is dedicated to the production of monofunctional PDMS and their application. However, the use of monofunctional PDMS in copolymerization reactions is rather limited.…”

Characterization and analysis of extended‐wear silicone hydrogel contact lenses utilizing novel silicone macromers

“…To increase oxygen transmissibility and reach acceptable lens hydrophilicity and water content, monomers with a relatively small number of branched siloxane groups forming pendent structures have typically been used rather than linear or large block polysiloxanes that could not achieve the needed hydrophilicity. Recent advances in living anionic ring‐opening polymerization of siloxanes have expanded both the range and precision of polysiloxanes as potential monomers for contact lenses 16 …”

“…Recent advances in living anionic ring-opening polymerization of siloxanes have expanded both the range and precision of polysiloxanes as potential monomers for contact lenses. 16 and monomethacryloxypropyl functional poly(trifluoropropyl) methylsiloxane, symmetric (MFS-M15, 800-1000 Da; Figure 1). All chemicals were used as received.…”

Cationic Polymerization of Hexamethylcyclotrisiloxane in Excess Water

“…Hexamethylcyclotrisiloxane is a monomer of choice when targeting silicone chains with perfectly controlled masses and functionality, as obtained by living anionic polymerization (for a very recent review, see an article just published in this Special Issue [ 7 ]). On the other hand, cationic polymerization of D 3 has been described mostly in the mid-eighties by two groups led by P. Sigwalt and J. Chojnowsky, and not further exploited (a summary of this more than 10 year’s competition can be found in [ 8 ]).…”