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1. Chemical recycling of poly(ethylene terephthalate) via sequential glycolysis, oleoyl chloride esterification and vulcanization to yield durable composites

   https://doi.org/10.1039/D2MA00986B  

   Lopez, Claudia V.; Smith, Rhett C. (July 2023, Materials Advances)

   Herein we report a method for the chemical recycling of poly(ethylene terephthalate) (PET) by a three-stage process employing sustainably-sourced organic materials and industrial byproduct sulfur. In this protocol, PET was subject to glycolysis with diethylene glycol to yield low molecular weight oligomers with hydroxyl end groups. The glycolyzed PET (GPET) was then reacted with oleoyl chloride to yield esterified PET (EPET) containing vulcanizable olefin units. The oligomers constituting GPET and EPET were elucidated by MALDI-TOF spectrometry. EPET underwent inverse vulcanization with elemental sulfur (90 wt%) for 35 min or 24 h to yield xPES or mPES, respectively. The composition, thermal, morphological, thermal and mechanical properties were characterized. The composites exhibited good to excellent mechanical properties that were improved significantly by extending the reaction time from 35 min used to prepare xPES (compressive strength = 10.5 MPa, flexural strength = 2.7 MPa) to 24 h used to prepare mPES (compressive strength = 26.9 MPa, flexural strength = 7.7 MPa). Notably, the compressive and flexural strengths of mPES represent 158% and 208% of the values required for residential building foundations made from traditional materials such as ordinary Portland cement. The three-stage approach delineated herein thus represents a way to mediate chemical recycling of waste plastic with green coreagents to yield composites having mechanical properties competitive with existing commercial structural materials. 

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2. One‐pot method for upcycling polycarbonate waste to yield high‐strength, BPA ‐free composites

   https://doi.org/10.1002/pol.20230724  

   Derr, Katelyn M.; Smith, Rhett C. (December 2023, Journal of Polymer Science)

   Abstract Environmental damage caused by waste plastics and downstream chemical breakdown products is a modern crisis. Endocrine‐disrupting bisphenol A (BPA), found in breakdown products of poly(bisphenol A carbonate) (PC), is an especially pernicious example that interferes with the reproduction and development of a wide range of organisms, including humans. Herein we report a single‐stage thiocracking method to chemically upcycle polycarbonate using elemental sulfur, a waste product of fossil fuel refining. Importantly, this method disintegrates bisphenol A units into monoaryls, thus eliminating endocrine‐disrupting BPA from the material and from any potential downstream waste. Thiocracking of PC (10 wt%) with elemental sulfur (90 wt%) at 320 °C yields the highly crosslinked networkSPC₉₀. The composition, thermal, morphological, and mechanical properties ofSPC₉₀were characterized by FT‐IR spectroscopy, TGA, DSC, elemental analysis, SEM/EDX, compressive strength tests, and flexural strength tests. The compositeSPC₉₀(compressive strength = 12.8 MPa, flexural strength = 4.33 MPa) showed mechanical strengths exceeding those of commercial bricks and competitive with those of mineral cements. The approach discussed herein represents a method to chemically upcycle polycarbonate while deconstructing BPA units, and valorizing waste sulfur to yield structurally viable building materials that could replace less‐green legacy materials. 

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3. Green and Atom Economical Route to High Compressive Strength Lignin Oil-Sulfur Composites

   https://doi.org/10.1007/s10924-024-03287-5  

   Tisdale, Katelyn_A; Dona, Nawoda_L_Kapuge; Maladeniya, Charini_P; Smith, Rhett_C (April 2024, Journal of Polymers and the Environment)

   Abstract Lignin is the most abundant natural source of aromatics but remains underutilized. Elemental sulfur is a plentiful by-product of fossil fuel refining. Herein we report a strategy for preparing a durable composite by the one-pot reaction of elemental sulfur and lignin oil comprising lower molecular weight lignin derivatives. A lignin oil-sulfur composite (LOS₉₀) was prepared by reacting 10 wt. % lignin oil with 90 wt. % elemental sulfur. The composite could be remelted and reshaped over several cycles without loss of properties. Results from the study showed thatLOS₉₀has properties competitive with or exceeding values for commercial ordinary Portland cement and brick formulations. For example,LOS₉₀displayed impressive compressive strength (22.1 MPa) and flexural strength (5.7 MPa).LOS₉₀is prepared entirely from waste materials with 98.5% atom economy of composite synthesis, a lowEfactor of 0.057, and lignin char as the only waste product of the process for its preparation. These results suggest the potential applications of lignin and waste sulfur in the continuous efforts to develop more recyclable and sustainable materials. 

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4. Composites produced from waste plastic with agricultural and energy sector by‐products

   https://doi.org/10.1002/app.54828  

   Lopez, Claudia V.; Smith, Rhett C. (November 2023, Journal of Applied Polymer Science)

   Abstract A three‐stage route to chemically upcycle post‐consumer poly(ethylene terephthalate) (PET) to produce high compressive strength composites is reported. This procedure involves initial glycolysis with diethylene glycol to produce a mixture (GPET) comprising oligomers of 2–7 terephthalate units followed by trans/esterification of GPET with fatty acid chains supplied by brown grease, an agricultural by‐product of animal fat of relatively low nutritional or fuel value. This process yields PGB comprising a mixture of mono‐terephthalate ester derivatives. The olefin units provided by unsaturated fatty acid chains in brown grease were crosslinked by an inverse vulcanization reaction with elemental sulfur to give composites GBS_x(x = wt% S, varied from 80%–90%). The compressive strengths of GBS₈₀(27.5 ± 2.6 MPa) and GBS₉₀(19.2 ± 0.8 MPa) exceed the compressive strength required of ordinary Portland cement (17 MPa) for its use in residential building foundations. The current route represents a way to repurpose waste plastic, energy sector by‐product sulfur, and agricultural by‐product brown grease to give high strength composites with mechanical properties suggesting their possible use to replace less sustainably sourced legacy structural materials. 

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5. Robust, remeltable and remarkably simple to prepare biomass–sulfur composites

   https://doi.org/10.1039/d0ma00538j  

   Lauer, Moira K.; Karunarathna, Menisha S.; Tennyson, Andrew G.; Smith, Rhett C. (October 2020, Materials Advances)

   null (Ed.)

   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. 

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