Polymer cements by copolymerization of waste sulfur, oleic acid, and pozzolan cements

Inverse vulcanization of octenyl succinate-modified corn starch as a route to biopolymer–sulfur composites

“…[27][28][29][30][31] Similar HSMs can be prepared from the reaction of aryl halides or anisole derivatives with sulfur as well, although polymerization of these monomers proceeds via different mechanisms than simple inverse vulcanization. [32][33][34][35] In addition to the aforementioned applications of HSMs, our group has recently reported numerous high-strength composite materials prepared by the reaction of sulfur with bio-derived monomers including fatty acids, [36][37][38][39] triglycerides, 42 terpenoids, 21,43 amino acid derivatives, 44 lignin derivatives, 22,35,45,46 cellulose derivatives, 3,21 and raw lignocellulosic biomass sources. 40,41 In terms of commercialization of biopolymer-derived materials, starch-derived films and composites have recently gained tremendous interest because starch is remarkably simple to solubilize, derivatize and process compared to cellulose.…”

A role for terpenoid cyclization in the atom economical polymerization of terpenoids with sulfur to yield durable composites

“…Materials made by inverse vulcanization can be durable polymers or composites in which polymeric sulfur domains, typically unstable at STP, are trapped and stabilized by the crosslinked network. Inverse vulcanization has proven successful for producing materials from a range of petrochemical and renewably-sourced olefins, 8 including terpenoids, [11][12][13][14][15] triglycerides, [16][17][18][19][20][21][22][23] fatty acids, [24][25][26][27] sorbitan esters, 28 amino acid derivatives, 29 guaiacol derivatives, 30 and cellulose/lignin derivatives. [31][32][33][34] Many applications for resulting materials have been noted, 35,36 as highlighted in the aforementioned references.…”

“…The Smith group has recently explored strategies for preparing biomass-derived sulfur composites made from organic small molecules, traditional petrochemical composites, biocomposites, and amino acid-based monomers with a primary goal of developing durable structural materials. [25][26][27]29,[31][32][33][34][43][44][45] These composites have shown mechanical strength profiles that in some cases outperform commercial building materials such as glass fibre-reinforced polymer composites or Portland cement. Unfortunately, some of these sulfur composites require several steps for monomer synthesis, detracting from the atom economy, greenness, and affordability of the processes.…”

Sequential crosslinking for mechanical property development in high sulfur content composites

“…High sulfur-content materials (HSMs) can be conveniently prepared by the reaction of elemental sulfur with olefins by inverse vulcanization (InV) [1][2][3] or from aryl halides by radical-induced aryl halide-sulfur polymerization (RASP, Scheme 1). [4][5][6] HSMs produced by these routes have been proposed for applications such as electrode materials, [7][8][9][10][11][12] lenses for thermal imaging, [13] fertilizers [14,15] absorbents for removing toxins from water, [16][17][18][19][20][21] or as structural materials [22][23][24][25][26][27][28][29] and thermal insulators. [30,31] The InV mechanism proceeds when olefins are crosslinked by their reaction with sulfur radicals produced by heating elemental sulfur to >159 C. RASP involves thermal reaction of aryl halides with elemental sulfur whereby S C aryl bonds are formed, a process requiring slightly higher temperatures of 220-250 C.…”

“…[32][33][34][35] Polymeric sulfur domains can reform following their rearrangement by metathesis when the material is cooled back to room temperature, provided that the supporting network is intact , allowing materials to be reshaped or thermally healed. [6,22,26,[36][37][38][39][40] Two types of S S bonds are typically present in these materials: those in polymeric/oligomeric catenates that undergo metathesis at temperatures as low as 90 C and those in cyclic S 8 allotropes that generally require heating to above 159 C to undergo metathesis. In the absence of other species, the polymeric sulfur radicals are stable up until around 250 C, when a color change from red to black is noted.…”