Rancid animal fats unsuitable for human or animal food production represent low‐value and abundant, yet underexploited organic chemical precursors. The current work describes a strategy to synthesize high sulfur‐content materials (HSMs) that directly utilizes a blend of partially hydrolyzed chicken fat and plant oils as the organic comonomers, following up on analogous reactions using brown grease in place of chicken fat. The reaction of sulfur and chicken fat with either canola or sunflower oil yielded crosslinked polymer composites CFSxor GFSx, respectively (
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
- NSF-PAR ID:
- 10472834
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Applied Polymer Science
- Volume:
- 141
- Issue:
- 3
- ISSN:
- 0021-8995
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract x = wt% sulfur, varied from 85%–90%). The composites exhibited compressive strengths of 24.7–31.7 MPa, and flexural strengths of 4.1–5.7 MPa, exceeding the value of established construction materials like ordinary Portland cement (compressive strength ≥17 MPa required for residential building, flexural strength 2–5 MPa). The composites also exhibited thermal stability up to 215–224 °C. The simple single‐step protocol described herein represents a way to upcycle an affordable and previously unexploited animal fat resource to form structural composites via the atom economical inverse vulcanization mechanism. -
more » « less
Abstract Here are reported composites made by crosslinking unsaturated units in canola, sunflower, or linseed oil with sulfur to yield
CanS ,SunS , andLinS , respectively. These plant oils were selected because the average number of crosslinkable unsaturated units per triglyceride vary from 1.3 for canola to 1.5 for sunflower and 1.8 for linseed oil. The remeltable composites show compressive strengths that increase with increasing unsaturation number fromCanS (9.3 MPa) toSunS (17.9 MPa) toLinS (22.9 MPa). These values forSunS andLinS are competitive when compared with the value of 17 MPa required for residential building using traditional Portland cement. The plant oil composites are recyclable over many cycles and can retain up to 100% of strength after 24 hr in oxidizing acid under conditions where Portland cement is dissolved in under 30 min. Infusion of the composites into premade cement blocks affords them with significantly improved acid resistance as well. This work thus provides a simple, nearly 100% atom economical route to convert plant oils and waste sulfur to composites having enhanced performance over commercial structural materials. -
more » « less
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 network
SPC 90 . The composition, thermal, morphological, and mechanical properties ofSPC 90 were characterized by FT‐IR spectroscopy, TGA, DSC, elemental analysis, SEM/EDX, compressive strength tests, and flexural strength tests. The compositeSPC 90 (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. -
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.more » « less
-
Sulfur cements have drawn significant attention as binders because sulfur is a byproduct of fossil fuel refining. Sulfur cements that can be formed by the vulcanization of elemental sulfur and plant-derived olefins such as terpenoids are particularly promising from a sustainability standpoint. A range of terpenoid–sulfur cements have shown compressional and flexural properties exceeding those of some commercial structural mineral cements. Pozzolans such as fly ash (FA), silica fume (SF), and ground granulated blast furnace slag (GGBFS) and abundant clay resources such as metakaolin (MK) are attractive fines for addition to binders. Herein, we report 10 composites prepared by a combination of sulfur, terpenoids (geraniol or citronellol), and these pozzolans. This study reveals the extent to which the addition of the pozzolan fines to the sulfur–terpenoid cements influences their mechanical properties and chemical resistance. The sulfur–terpenoid composites CitS and GerS were prepared by the reaction of 90 wt% sulfur and 10 wt% citronellol or geraniol oil, respectively. The density of the composites fell within the range of 1800–1900 kg/m3 and after 24 h submersion in water at room temperature, none of the materials absorbed more than 0.7 wt% water. The compressional strength of the as-prepared materials ranged from 9.1–23.2 MPa, and the percentage of compressional strength retained after acid challenge (submersion in 0.1 M H2SO4 for 24 h) ranged from 80–100%. Incorporating pozzolan fines into the already strong CitS (18.8 MPa) had negligible effects on its compressional strength within the statistical error of the measurement. CitS-SF and CitS-MK had slightly higher compressive strengths of 20.4 MPa and 23.2 MPa, respectively. CitS-GGBFS and CitS-FA resulted in slightly lower compressive strengths of 17.0 MPa and 15.8 MPa, respectively. In contrast, the compressional strength of initially softer GerS (11.7 MPa) benefited greatly after incorporating hard mineral fines. All GerS derivatives had higher compressive strengths than GerS, with GerS-MK having the highest compressive strength of 19.8 MPa. The compressional strengths of several of the composites compare favorably to those required by traditional mineral cements for residential building foundations (17 MPa), whereas such mineral products disintegrate upon similar acid challenge.more » « less
