Functionalized chalcogenide hybrid inorganic/organic polymers (CHIPs) via inverse vulcanization of elemental sulfur and vinylanilines

Abstract

The first example of a sulfur copolymer with amine groups poly(sulfur-random-vinylaniline) was synthesized and successfully post-functionalized to improve the thermomechanical properties of these materials.

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 .…”

“…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)] .…”

“…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)] . More recently, we reported on the inverse vulcanization of sulfur with 4‐vinylaniline (4‐VA) which proceeded with a profound enhancement of polymerization rate which was attributed to polarity reversal effects [Scheme (b)] …”

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.…”

Synthesis of Chiral Sulfur‐Containing Polymers: Asymmetric Copolymerization of meso‐Epoxides and Carbonyl Sulfide

“…[1] Va rious sulfur-containing polymers,f or example,p oly(thioether)s, [2] poly(thiourethane)s, [3] poly(thioester)s, [4] poly(sulfurrandom-styrene), [5] and poly(thiocarbonate)s [6] have been produced. [1] Va rious sulfur-containing polymers,f or example,p oly(thioether)s, [2] poly(thiourethane)s, [3] poly(thioester)s, [4] poly(sulfurrandom-styrene), [5] and poly(thiocarbonate)s [6] have been produced.…”