skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Polybutadiene Modification of Brown Grease‐Sulfur Materials
ABSTRACT High sulfur‐content materials (HSMs) prepared via inverse vulcanization are attractive for a range of sustainable material applications, particularly when synthesized from waste‐derived feedstocks such as brown grease (BG). Two BG‐based composites,SunBG90andaBG90, were prepared using elemental sulfur and either native or allylated brown grease, respectively. This study explores the effect of reinforcing these sulfur‐rich networks with low loadings (0.5–2 wt. %) of highcis‐1,4‐content liquid polybutadiene (PBD). Incorporation of PBD resulted in significant increases in storage modulus, with a near‐linear relationship between PBD content and stiffness enhancement for both material types. At −60°C, storage modulus increased more than fivefold foraBG90and more than tripled forSunBG90. In contrast, flexural strength and flexural modulus exhibited non‐linear responses, with diminishing or reversed gains at higher PBD loadings, suggesting limits to rubber domain compatibility and dispersion. Thermal analysis confirmed high decomposition temperatures (212°C–226°C) and stable glass transitions, indicating thermal robustness of the reinforced networks. Compared with previous studies requiring higher PBD loadings, these results demonstrate that BG‐based HSMs can be effectively reinforced at low additive levels, offering mechanically robust, low‐cost, and renewable alternatives for structural applications.  more » « less
Award ID(s):
2203669
PAR ID:
10647780
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Polymer Science
Volume:
63
Issue:
22
ISSN:
2642-4150
Format(s):
Medium: X Size: p. 4740-4747
Size(s):
p. 4740-4747
Sponsoring Org:
National Science Foundation
More Like this
  1. ABSTRACT Brown grease (BG) is a high‐free fatty acid (FFA) waste coproduct from the food industry that remains largely unexploited. Herein, we describe a design strategy to upcycle BG into high sulfur‐content materials (HSMs) via inverse vulcanization, circumventing the need for costly transition metals or food‐grade compatibilizers. First, BG was esterified with methyl or allyl groups, yielding MeBG and aBG, respectively. This modification masked the polar carboxylic acids and enhanced miscibility with molten sulfur. Subsequent inverse vulcanization produced remeltable HSMs at 80 or 90 wt% sulfur with uniform elemental distributions by SEM–EDX. FT‐IR spectroscopy revealed the consumption of C=C moieties and the formation of C–S bonds, signifying robust cross‐linking. Thermal analysis (TGA, DSC) indicated good thermal stability (Td,5%up to 223°C) and glass transitions characteristic of polysulfide networks. Mechanical evaluations demonstrated compressive strengths up to 19.2 MPa, exceeding the minimum requirement for residential foundation‐grade cement (17 MPa) and rivaling previously reported HSMs containing similarly high sulfur content. Notably, MeBG and aBG incorporate organics comprising up to 97 wt% BG, significantly improving the upcycled mass efficiency relative to earlier BG‐based composites. This esterification‐driven approach thus offers a practical, scalable pathway to convert low‐value BG into advanced materials with tunable thermomechanical properties. 
    more » « less
  2. Abstract The valorization of waste‐derived feedstocks for polymer synthesis represents a sustainable alternative to petroleum‐based materials. In this study, brown grease, a low‐value waste lipid source, is utilized as a precursor for polyol monomer synthesis via a two‐step functionalization process. Transesterification of brown grease with allyl alcohol generates allyl esters, which are subsequently modified via thiol‐ene click chemistry with 2‐mercaptoethanol to yield hydroxyl‐functionalized polyols (BG‐diol). The thiol‐ene reaction proceeds under mild UV‐initiated conditions, achieving high conversion efficiency (>90%) while preserving the structural integrity of the derived polyol.BG‐diolis further polymerized with 4,4′‐methylene diphenyl diisocyanate (MDI) through step‐growth polymerization to form brown grease‐derived polyurethane (BG‐PU). Comparative analysis ofBG‐PUwith polyurethane (PU) synthesized from purified oleic acid (OLA‐PU) demonstrates comparable molecular weight distributions (Mn = 14.4 kDa,Mw = 20.4 kDa forBG‐PU) and thermal properties (Tg = 24 °C,Td,5%= 270 °C forBG‐PU). These results underscore the feasibility of brown grease as a cost‐effective and renewable alternative to plant oil‐based polyols, offering a pathway toward sustainable PU production while mitigating food security concerns. This approach exemplifies the potential of waste lipids in circular economy strategies for high‐performance polymer synthesis. 
    more » « less
  3. Abstract 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 (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
  4. Abstract Herein high-strength composites are prepared from elemental sulfur, sunflower oil, and wastewater sludge. Fats extracted from dissolved air flotation (DAF) solids were reacted with elemental sulfur to yield compositeDAFS(10 wt% DAF fats and 90 wt% sulfur). Additional composites were prepared from DAF fat, sunflower oil and sulfur to giveSunDAFx(x = wt% sulfur, varied from 85–90%). The composites were characterized by spectroscopic, thermal, and mechanical methods. FT-IR spectra revealed a notable peak at 798 cm–1indicating a C–S stretch inDAFS,SunDAF90, andSunDAF85indicating successful crosslinking of polymeric sulfur with olefin units. SEM/EDX analysis revealed homogenous distribution of carbon, oxygen, and sulfur inSunDAF90andSunDAF85. The percent crystallinity exhibited byDAFS(37%),SunDAF90(39%), andSunDAF85(45%) was observed to be slightly lower than that of previous composites prepared from elemental sulfur and fats and oils.DAFSandSunDAFxdisplayed compressive strengths (26.4–38.7 MPa) of up to 227% above that required (17 MPa) of ordinary Portland cement for residential building foundations. The composite decomposition temperatures ranged from 211 to 219 °C, with glass transition temperatures of − 37 °C to − 39 °C. These composites thus provide a potential route to reclaim wastewater organics for use in value-added structural materials having mechanical properties competitive with those of commercial products. 
    more » « less
  5. 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. 
    more » « less