Chalcogenide hybrid inorganic/organic polymers (CHIPs) via inverse vulcanization and dynamic covalent polymerizations

Abstract

Poly(sulfur-random-styrene) was made via inverse vulcanization and used for dynamic covalent copolymerization (DCP) to incorporate novel vinylic monomers.

Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid

“…Inverse vulcanization (Scheme ) has emerged as an intriguing approach to valorizing agricultural waste through the combination of sulfur with plant‐derived olefins . The sulfur used in the inverse vulcanization process is itself a waste product from desulfurization of fossil fuels, so when sustainably sourced waste product olefins are employed the materials achieved can be comprised entirely of waste products.…”

Nucleophilic Activation of Elemental Sulfur for Inverse Vulcanization and Dynamic Covalent Polymerizations

“…Toward this end, we developed a facile, one‐step polymerization process, termed inverse vulcanization that utilizes molten sulfur as the reaction medium and comonomer for free‐radical copolymerization with 1,3‐diisopropenyl‐benzene (DIB) and other unsaturated comonomers to afford chemically stable and processable high sulfur content copolymers . The inverse vulcanization process affords a new class of polymeric materials, termed, chalcogenide hybrid inorganic/organic polymers (CHIPs) which we demonstrated can incorporate sulfur (S), selenium (Se), and organic vinylic comonomers to prepare hybrid materials . These polymeric materials were proven to have useful electrochemical and optical properties and were integrated into devices that exploit these useful features .…”

“…S2). The floor temperature of this DCP process was found to be 110 °C due to the lower bond dissociation energy of polysulfides and expanded the scope of comonomers available that could be incorporated into CHIPs materials . However, there remain opportunities and challenges to develop improved methods and catalytic systems to enable polymerizations of S 8 at lower temperatures and with other functional comonomers.…”

“…To date, we have developed variations of the inverse vulcanization process to enhance the rate of polymerizations and introduce side chain functionality to CHIPs materials prepared from these processes . In our initial bulk polymerizations for the inverse vulcanization of sulfur with DIB, we proposed a classical, homolytic ring‐opening mechanism for the generation of primary sulfur radicals which undergo thiol–ene additions to form the copolymer [Scheme (a)] .…”

Chalcogenide hybrid inorganic/organic polymer resins: Amine functional prepolymers from elemental sulfur

“…The concept of utilizing elemental sulfur (S 8 ) as an alternative feedstock for the synthesis of polymeric materials has been widely explored in the past decade . Polymeric materials derived from the polymerization of elemental sulfur constitute an intriguing new class of sulfur‐containing polymers and polysulfides, which have been referred to as chalcogenide hybrid inorganic/organic polymers (CHIPs) . One of the most widely used methods for preparing CHIPs has been the use of the inverse vulcanization process, where liquid sulfur is employed as the solvent and monomer in a homolytic ring‐opening copolymerization with organic comonomers.…”