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

Abstract

Terpenoid cyclization reactions were observed in the course of reacting terpenes and sulfur to yield durable composites.

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.…”

Influence of Component Ratio on Thermal and Mechanical Properties of Terpenoid-Sulfur Composites

“…noids geraniol and farnesol underwent intramolecular cyclization reactions in addition to the expected inverse vulcanization shown in Scheme 1 [10]. Microstructures for the geraniol-sulfur composites GerSx and farnesol-sulfur composites FarSx (x = wt % S in the monomer feed) were thus determined to be those shown in Scheme 2.…”

“…Preparation of terpenoid-sulfur composites was accomplished by the reaction of each terpenoid with molten elemental sulfur at 180 • C for 35 min in the absence of any other added solvents or reagents according to the procedure we previously reported for the preparation of GerS 90 and FarS 90 [10]. Reactions of farnesol with 5, 10, 15, 20, 30, 40 and 50 wt % sulfur all produced rigid homogeneous solids FarS x (x = wt % S) ranging in color from brown to black (Figure 1).…”

“…Terpenoids are biologically-sourced olefins that hold great promise for supplanting fossil fuel-derived olefins in tars and bitumen used in asphalt, in polymers, and in related composite materials [1][2][3][4][5][6][7][8][9]. In previous work we demonstrated that monoalkene, diene and triene terpenoids react with sulfur to yield durable composites having compressive strengths that can exceed that of ordinary Portland cement (OPC) [10,11]. Sulfur is a waste product of fossil fuel refining, and significant efforts have been made to uncover value-added applications for it [12][13][14][15][16][17][18].…”

Morphological and mechanical characterization of high-strength sulfur composites prepared with variably-sized lignocellulose particles

“…To meet this goal the organic component to be reacted with waste sulfur must be renewably-sourced and preferably carbon negative to minimize or eliminate contributions to CO 2 emission. Towards this end, researchers have demonstrated successful HSM production by reacting sulfur with fatty acids, 25,31,33 terpenoids, 19,21,57,[73][74][75] starch, 18,24 lignin, 12,17,28,29 cellulose, 13,19 and lignocellulosic biomass derivatives. 16,17 Some of those biologically-derived materials do not possess the olefin functionalities needed for inverse vulcanization and therefore require derivatization or use of alternative reaction strategies.…”