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: From Petroleum to Biobased Crude: A Thermoplastic Polyurethane from Lignin-oil without Isocyanates
The movement to transfer from petroleum-based products and materials to renewables does not necessarily have to bypass the use of oil. A new type of “black-gold” is readily abundant from the earth’s most abundant source of aromatic carbon: lignin. While fractionation of petroleum yields fuels and chemicals for a diverse set of industries, lignin fractionation using targeted catalysts has demonstrated the ability to generate monomers and oligomers rich in functional groups for polymer synthesis. This study explores the use of lignin-oil, generated from reductive catalytic fractionation of popular wood, to a hydroxyl-rich mixture of aromatics that is used to synthesize a thermoplastic non-isocyanate polyurethane. The lignin-oil is first converted to a cyclocarbonated derivative using a benign synthetic sequence and further polymerized with a diamine to yield the non-isocyanate TPU. While more work is underway to optimize the reaction conditions and meet typical mechanical properties of commercial materials, initial analysis shows thermoplastic behavior and flexible properties consistent with traditional thermoplastic polyurethanes.  more » « less
Award ID(s):
2122822
PAR ID:
10354766
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
ANTEC 2022
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Lignin is the most abundant aromatic biopolymer and is the sustainable feedstock most likely to supplant petroleum-derived aromatics and downstream products. Rich in functional groups, lignin is largely peerless in its potential for chemical modification towards attaining target properties. Lignin’s crosslinked network structure can be exploited in composites to endow them with remarkable strength, as exemplified in timber and other structural elements of plants. Yet lignin may also be depolymerized, modified, or blended with other polymers. This review focuses on substituting petrochemicals with lignin derivatives, with a particular focus on applications more significant in terms of potential commercialization volume, including polyurethane, phenol-formaldehyde resins, lignin-based carbon fibers, and emergent melt-processable waste-derived materials. This review will illuminate advances from the last eight years in the prospective utilization of such lignin-derived products in a range of application such as adhesives, plastics, automotive components, construction materials, and composites. Particular technical issues associated with lignin processing and emerging alternatives for future developments are discussed. 
    more » « less
  2. The structural similarities between lignin-derivable bisguaiacols and petroleum-derived bisphenol A/F (BPA/BPF) suggest that bisguaiacols could be ideal biobased alternatives to BPA/BPF in non-isocyanate polyurethane (NIPU) thermosets. Herein, bisguaiacol/bisphenol-derived cyclic carbonates with variations in methoxy content and bridging-carbon substitution were cured with two triamines of different chain lengths, and the impact of these differences on the thermomechanical properties of NIPU networks was examined. The methoxy groups present in the lignin-derivable cyclic carbonates led to thermosets with significantly improved toughness (∼49–59 MJ m −3 ) and elongation at break ( ε b ∼195–278%) vs. the BPA/BPF-based benchmarks (toughness ∼ 26–35 MJ m −3 , ε b ∼ 86–166%). Furthermore, the addition of dimethyl substitution on the bridging carbon resulted in increased yield strength ( σ y ) – from ∼28 MPa for networks with unsubstituted bridging carbons to ∼45 MPa for the dimethyl-substituted materials. These enhancements to mechanical properties were achieved while retaining essential thermoset properties, such as application-relevant moduli and thermal stabilities. Finally, the triamine crosslinkers provided substantial tunability of thermomechanical properties and produced NIPUs that ranged from rigid materials with a high yield strength ( σ y ∼ 65–88 MPa) to flexible and tough networks. Overall, the structure-property relationships presented highlight a promising framework for the design of versatile, bio-derivable, NIPU thermosets. 
    more » « less
  3. 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. 
    more » « less
  4. Non-toxic resins formulated with renewable components have been receiving increased attention as sustainable alternatives to petroleum-based resins. In this work, we demonstrate a new class of lignin-amino acid (LA) resins, formulated with non-toxic components that are abundant and can be renewably sourced from field leftovers (corn cobs) and lysine (from bio-based sugars). NMR (1H, 31P, 13C-1H HSQC, 15N-1H HSQC, and 15N-1H HMBC), FTIR, thermogravimetric, gel permeation chromatography and elemental analyses provide insights into the physicochemical properties of the resins, including the presence of LA linkages such as C-N cross linking. The LA resin creates strong bonds between pieces of wood, metals (aluminum and stainless steel) and plastics. Internal bond strengths (IBS) of balsa wood and medium density fiberboard specimens glued with LA resins, measured using an Instron instrument, were comparable to those bonded with commercial polyurethane (PU) and polyvinyl acetate (PVAc) resins. Resins prepared with ozone-pretreated lignin have significantly larger molar masses and display increased bond strengths with glued substates as inferred from IBS measurements. This is attributed to the creation of reactive oxygen-based functionalities in the lignin upon ozone pretreatment. Lignin-amino acid resins thus show promise as a feasible and sustainable alternative to petroleum-based resins. 
    more » « less
  5. Lignin is the second-most abundant biopolymer in nature and remains a severely underutilized waste product of agriculture and paper production. Sulfur is the most underutilized byproduct of petroleum and natural gas processing industries. On their own, both sulfur and lignin exhibit very poor mechanical properties. In the current work, a strategy for preparing more durable composites of sulfur and lignin, LSx , is described. Composites LSx were prepared by reaction of allyl lignin with elemental sulfur, whereby some of the sulfur forms polysulfide crosslinks with lignin to yield a three-dimensional network. Even relatively small quantities (<5 wt%) of the polysulfide-crosslinked lignin network provides up to a 3.4-fold increase in mechanical reinforcement over sulfur alone, as measured by the storage moduli and flexural strength determined from dynamic mechanical analysis (temperature dependence and stress–strain analysis). Notably, LSx composites could be repeatedly remelted and recast after pulverization without loss of mechanical strength. These initial studies suggest potential practical applications of lignin and sulfur waste streams in the ongoing quest towards more sustainable, recyclable structural materials. 
    more » « less