Title: Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials
High sulfur-content materials (HSMs) have been investigated for a plethora of applications owing to a combination of desirable properties and the low cost of waste sulfur as a starting monomer. Whereas extended sulfur catenates are unstable with respect to orthorhombic sulfur (S 8 rings) at STP, oligomeric/polymeric sulfur chains can be stabilized when they are confined in a supporting matrix. The vast majority of reported HSMs have been made by inverse vulcanization of sulfur and olefins. In the current case, a radical aryl halide–sulfur polymerization (RASP) route was employed to form an HSM ( XS81 ) by copolymerizing elemental sulfur with the xylenol derivative 2,4-dimethyl-3,5-dichlorophenol (DDP). XS81 is a composite of which 81 wt% is sulfur, wherein the sulfur is distributed between cross-linking chains averaging four sulfur atoms in length and trapped sulfur that is not covalently attached to the network. XS81 (flexural strength = 2.0 MPa) exhibits mechanical properties on par with other HSMs prepared by inverse vulcanization. Notably, XS81 retains mechanical integrity over many heat-recast cycles, making it a candidate for facile recyclability. This is the first report of an HSM comprising stabilized polymeric sulfur that has been successfully prepared from a small molecular comonomer by RASP. Preparation of XS81 thus demonstrates a new route to access HSMs using small molecular aryl halides, a notable expansion beyond the olefins required for the well-studied inverse vulcanization route to HSMs from small molecular comonomers. more »« less
Karunarathna, Menisha S.; Tennyson, Andrew G.; Smith, Rhett C.(
, Journal of Materials Chemistry A)
null
(Ed.)
This report introduces a new approach to high sulfur-content materials. This route, RASP (radical-induced aryl halide/sulfur polymerization), expands the substrate scope beyond olefins required for the traditional inverse vulcanization route to such materials. RASP allows direct reaction of two unmodified industrial waste products to give lignin–sulfur composites.
Fossil fuel refining produces over 70 Mt of excess sulfur annually from for which there is currently no practical use. Recently, methods to convert waste sulfur to recyclable and biodegradable polymers have been delineated. In this report, a commercial bisphenol A (BPA) derivative, 2,2′,5,5′-tetrabromo(bisphenol A) (Br4BPA), is explored as a potential organic monomer for copolymerization with elemental sulfur by RASP (radical-induced aryl halide-sulfur polymerization). Resultant copolymers, BASx (x = wt% sulfur in the monomer feed, screened for values of 80, 85, 90, and 95) were characterized by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Analysis of early stage reaction products and depolymerization products support proposed S–Caryl bond formation and regiochemistry, while fractionation of BASx reveals a sulfur rank of 3–6. Copolymers having less organic cross-linker (5 or 10 wt%) in the monomer feed were thermoplastics, whereas thermosets were accomplished when 15 or 20 wt% of organic cross-linker was used. The flexural strengths of the thermally processable samples (>3.4 MPa and >4.7 for BAS95 and BAS90, respectively) were quite high compared to those of familiar building materials such as portland cement (3.7 MPa). Furthermore, copolymer BAS90 proved quite resistant to degradation by oxidizing organic acid, maintaining its full flexural strength after soaking in 0.5 M H2SO4 for 24 h. BAS90 could also be remelted and recast into shapes over many cycles without any loss of mechanical strength. This study on the effect of monomer ratio on properties of materials prepared by RASP of small molecular aryl halides confirms that highly cross-linked materials with varying physical and mechanical properties can be accessed by this protocol. This work is also an important step towards potentially upcycling BPA from plastic degradation and sulfur from fossil fuel refining.
Lignocellulosic biomass holds a tremendous opportunity for transformation into carbon-negative materials, yet the expense of separating biomass into its cellulose and lignin components remains a primary economic barrier to biomass utilization. Herein is reported a simple procedure to convert several biomass-derived materials into robust, recyclable composites through their reaction with elemental sulfur by inverse vulcanization, a process in which olefins are crosslinked by sulfur chains. In an effort to understand the chemistry and the parameters leading to the strength of these composites, sulfur was reacted with four biomass-derivative comonomers: (1) unmodified peanut shell powder, (2) allyl peanut shells, (3) ‘mock’ allyl peanut shells (a mixture containing independently-prepared allyl cellulose and allyl lignin), or (4) peanut shells that have been defatted by extraction of peanut oil. The reactions of these materials with sulfur produce the biomass–sulfur composites PSx , APSx , mAPSx and dfPSx , respectively, where x = wt% sulfur in the monomer feed. The influence of biomass : sulfur ratio was assessed for PSx and APSx . Thermal/mechanical properties of composites were evaluated for comparison to commercial materials. Remarkably, unmodified peanut shell flour can simply be heated with elemental sulfur to produce composites having flexural/compressive strengths exceeding those of Portland cement, an effect traced to the presence of olefin-bearing peanut oil in the peanut shells. When allylated peanut shells are used in this process, a composite having twice the compressive strength of Portland cement is attained.
Graham, Matthew J.; Lopez, Claudia V.; Maladeniya, Charini P.; Tennyson, Andrew G.; Smith, Rhett C.(
, Journal of Applied Polymer Science)
Abstract
Low cost and high durability have made Portland cement the most widely‐used building material, but benefits are offset by environmental harm of cement production contributing 8–10% of total anthropogenic CO2gas emissions. High sulfur‐content materials (HSMs) are an alternative that can perform the binding roles as cements with a smaller carbon footprint, and possibly superior chemical, physical, and mechanical properties. Inverse vulcanization of 90 wt% sulfur with 10 wt% canola oil or sunflower oil to yield CanS or SunS, respectively. Notably, these HSMs prepared at temperatures ≤180 °C compared to >1200 °C hours for Portland cement CanS was combined with 5 wt% fly ash (FA), silica fume (SF), ground granulated blast furnace slag (GGBFS), or metakaolin (MK) to give composites CanS‐FA, CanS‐SF, CanS‐GGBFS, and CanS‐MK, respectively. The analogous protocol with SunS likewise yielded SunS‐FA, SunS‐SF, SunS‐GGBFS, and SunS‐MK. Each of these HSMs exhibit high compressive mechanical strength, low water uptake values, and exceptional resistance to acid‐induced corrosion. All of the composites also exhibit superior compressive strength retention after exposure to acidic solutions, conditions under which Portland cement undergoes dissolution. The polymer cement‐pozzolan composites reported herein may thus serve as greener alternatives to traditional Portland cement in some applications.
The search for alternative feedstocks to replace petrochemical polymers has centered on plant-derived monomer feedstocks. Alternatives to agricultural feedstock production should also be pursued, especially considering the ecological damage caused by modern agricultural practices. Herein, l -tyrosine produced on an industrial scale by E. coli was derivatized with olefins to give tetraallyltyrosine. Tetraallyltyrosine was subsequently copolymerized via its inverse vulcanization with industrial by-product elemental sulfur in two different comonomer ratios to afford highly-crosslinked network copolymers TTSx ( x = wt% sulfur in monomer feed). TTSx copolymers were characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis (DMA). DMA was employed to assess the viscoelastic properties of TTSx through the temperature dependence of the storage modulus, loss modulus and energy damping ability. Stress–strain analysis revealed that the flexural strength of TTSx copolymers (>6.8 MPa) is more than 3 MPa higher than flexural strengths for previously-tested inverse vulcanized biopolymer derivatives, and more than twice the flexural strength of some Portland cement compositions (which range from 3–5 MPa). Despite the high tyrosine content (50–70 wt%) in TTSx , the materials show no water-induced swelling or water uptake after being submerged for 24 h. More impressively, TTSx copolymers are highly resistant to oxidizing acid, with no deterioration of mechanical properties even after soaking in 0.5 M sulfuric acid for 24 h. The demonstration that these durable, chemically-resistant TTSx copolymers can be prepared from industrial by-product and microbially-produced monomers via a 100% atom-economical inverse vulcanization process portends their potential utility as sustainable surrogates for less ecofriendly materials.
Karunarathna, Menisha S., Lauer, Moira K., Tennyson, Andrew G., and Smith, Rhett C. Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials. Retrieved from https://par.nsf.gov/biblio/10199243. Polymer Chemistry 11.9 Web. doi:10.1039/c9py01706b.
Karunarathna, Menisha S., Lauer, Moira K., Tennyson, Andrew G., & Smith, Rhett C. Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials. Polymer Chemistry, 11 (9). Retrieved from https://par.nsf.gov/biblio/10199243. https://doi.org/10.1039/c9py01706b
Karunarathna, Menisha S., Lauer, Moira K., Tennyson, Andrew G., and Smith, Rhett C.
"Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials". Polymer Chemistry 11 (9). Country unknown/Code not available. https://doi.org/10.1039/c9py01706b.https://par.nsf.gov/biblio/10199243.
@article{osti_10199243,
place = {Country unknown/Code not available},
title = {Copolymerization of an aryl halide and elemental sulfur as a route to high sulfur content materials},
url = {https://par.nsf.gov/biblio/10199243},
DOI = {10.1039/c9py01706b},
abstractNote = {High sulfur-content materials (HSMs) have been investigated for a plethora of applications owing to a combination of desirable properties and the low cost of waste sulfur as a starting monomer. Whereas extended sulfur catenates are unstable with respect to orthorhombic sulfur (S 8 rings) at STP, oligomeric/polymeric sulfur chains can be stabilized when they are confined in a supporting matrix. The vast majority of reported HSMs have been made by inverse vulcanization of sulfur and olefins. In the current case, a radical aryl halide–sulfur polymerization (RASP) route was employed to form an HSM ( XS81 ) by copolymerizing elemental sulfur with the xylenol derivative 2,4-dimethyl-3,5-dichlorophenol (DDP). XS81 is a composite of which 81 wt% is sulfur, wherein the sulfur is distributed between cross-linking chains averaging four sulfur atoms in length and trapped sulfur that is not covalently attached to the network. XS81 (flexural strength = 2.0 MPa) exhibits mechanical properties on par with other HSMs prepared by inverse vulcanization. Notably, XS81 retains mechanical integrity over many heat-recast cycles, making it a candidate for facile recyclability. This is the first report of an HSM comprising stabilized polymeric sulfur that has been successfully prepared from a small molecular comonomer by RASP. Preparation of XS81 thus demonstrates a new route to access HSMs using small molecular aryl halides, a notable expansion beyond the olefins required for the well-studied inverse vulcanization route to HSMs from small molecular comonomers.},
journal = {Polymer Chemistry},
volume = {11},
number = {9},
author = {Karunarathna, Menisha S. and Lauer, Moira K. and Tennyson, Andrew G. and Smith, Rhett C.},
editor = {null}
}
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