Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

Meng, Xianzhi; Zhang, Shuyang; Scheidemantle, Brent; Wang, Yun-yan; Pu, Yunqiao; Wyman, Charles E.; Cai, Charles M.; Ragauskas, Arthur J.

doi:10.1016/j.indcrop.2022.114579

Title: Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

Journal Article · 01 February 2022 · Industrial Crops and Products

DOI: https://doi.org/10.1016/j.indcrop.2022.114579 · OSTI ID:1844861

Meng, Xianzhi ^[1]; Zhang, Shuyang ^[1]; Scheidemantle, Brent ^[2]; Wang, Yun-yan ^[1];

^[3]; Wyman, Charles E. ^[2]; Cai, Charles M. ^[2];

^[4]

Univ. of Tennessee, Knoxville, TN (United States)
Univ. of California, Riverside, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Lignin is a major bioresource from 2nd generation biorefinery process streams and from pulp and paper production that is still severely underutilized nowadays. Its natural polymeric and aromatic structures make it suitable as a potential building block for biopolymer production. Due to the growing environmental and health concerns over conventional polyurethane (PU) manufacturing processes that utilize toxic isocyanates, there is a great interest to develop a non-isocyanate PU (NIPU) route. Herein, we demonstrate a novel strategy that uses highly pure lignin isolated from co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment of poplar wood to produce biobased NIPUs. In this strategy, hardwood poplar is firstly fractionated via a CELF pretreatment to produce a clean lignin stream that is rich in phenolics. The CELF lignin was then aminated by a Mannich reaction, and the aminated CELF lignin was finally reacted with bicyclic carbonates to yield an advanced NIPU. In this work, the structure, mechanical, and thermal properties of these novel NIPUs were elucidated by FTIR, NMR, tensile test, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The mechanical properties of these lignin based NIPUs could be tuned from highly rigid to elastic polymers by simply modifying the lignin constituents of the polymer. The thermal stabilities of NIPUs were improved because of the addition of aminated lignin, and NIPU containing 55 and 23 wt% lignin showed the highest tensile strength (~1.2 MPa) and elongation at break (~140%), respectively. The results obtained in this study demonstrate that the reaction of cyclic carbonate with aminated lignin represents an interesting pathway for the synthesizing of lignin based NIPU with a relative high lignin content.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDA; National Institute of Food and Agriculture (NIFA)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1844861

Journal Information:: Industrial Crops and Products, Journal Name: Industrial Crops and Products Journal Issue: 1 Vol. 178; ISSN 0926-6690

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO2 North, Michael; Pasquale, Riccardo Angewandte Chemie International Edition, Vol. 48, Issue 16 https://doi.org/10.1002/anie.200805451	journal	February 2009
Improving aging resistance and mechanical properties of waterborne polyurethanes modified by lignin amines Liu, Jun; Liu, Hai-Feng; Deng, Li Journal of Applied Polymer Science, Vol. 130, Issue 3 https://doi.org/10.1002/app.39267	journal	May 2013
Tuning the properties of segmented polyhydroxyurethanes via chain extender structure: ARTICLE Beniah, Goliath; Heath, William H.; Jeon, Junho Journal of Applied Polymer Science, Vol. 134, Issue 45 https://doi.org/10.1002/app.44942	journal	February 2017
Synthesis and characterization of elastomeric, biobased, nonisocyanate polyurethane from natural rubber Jaratrotkamjorn, Ruedee; Nourry, Arnaud; Pasetto, Pamela Journal of Applied Polymer Science, Vol. 134, Issue 42 https://doi.org/10.1002/app.45427	journal	July 2017
Lignin Bioproducts to Enable Biofuels Wyman, Charles E.; Ragauskas, Arthur J. Biofuels, Bioproducts and Biorefining, Vol. 9, Issue 5 https://doi.org/10.1002/bbb.1582	journal	September 2015
Challenging/interesting lignin times Ragauskas, Arthur J. Biofuels, Bioproducts and Biorefining, Vol. 10, Issue 5 https://doi.org/10.1002/bbb.1714	journal	August 2016
From the Synthesis of Biobased Cyclic Carbonate to Polyhydroxyurethanes: A Promising Route towards Renewable Non‐Isocyanate Polyurethanes Carré, Camille; Ecochard, Yvan; Caillol, Sylvain ChemSusChem, Vol. 12, Issue 15 https://doi.org/10.1002/cssc.201900737	journal	June 2019
A New Environmentally Friendly Approach to Lignin-Based Cyclic Carbonates Kühnel, Isabell; Saake, Bodo; Lehnen, Ralph Macromolecular Chemistry and Physics, Vol. 219, Issue 7 https://doi.org/10.1002/macp.201700613	journal	January 2018
Access to nonisocyanate poly(thio)urethanes: A comparative study Besse, Vincent; Foyer, Gabriel; Auvergne, Rémi Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 15 https://doi.org/10.1002/pola.26722	journal	May 2013
Reactivity of secondary amines for the synthesis of non-isocyanate polyurethanes Camara, Fatoumata; Benyahya, Sofia; Besse, Vincent European Polymer Journal, Vol. 55 https://doi.org/10.1016/j.eurpolymj.2014.03.011	journal	June 2014
Green polyurethane from lignin and soybean oil through non-isocyanate reactions Lee, Albert; Deng, Yulin European Polymer Journal, Vol. 63 https://doi.org/10.1016/j.eurpolymj.2014.11.023	journal	February 2015
Synthesis and characterization of advanced biobased thermoplastic nonisocyanate polyurethanes, with controlled aromatic-aliphatic architectures Carré, Camille; Zoccheddu, Hugo; Delalande, Stéphane European Polymer Journal, Vol. 84 https://doi.org/10.1016/j.eurpolymj.2016.05.030	journal	November 2016
Novel thermoplastic polyhydroxyurethane elastomers as effective damping materials over broad temperature ranges Beniah, Goliath; Liu, Kun; Heath, William H. European Polymer Journal, Vol. 84 https://doi.org/10.1016/j.eurpolymj.2016.05.031	journal	November 2016
Lignin inspired phenolic polyethers synthesized via ADMET: Systematic structure-property investigation Vlaminck, Laetitia; Lingier, Sophie; Hufendiek, Andrea European Polymer Journal, Vol. 95 https://doi.org/10.1016/j.eurpolymj.2017.08.042	journal	October 2017
Amination of biorefinery technical lignins using Mannich reaction synergy with subcritical ethanol depolymerization Wang, Bing; Chen, Tian-Ying; Wang, Han-Min International Journal of Biological Macromolecules, Vol. 107 https://doi.org/10.1016/j.ijbiomac.2017.09.012	journal	February 2018
Amination of biorefinery technical lignin by Mannich reaction for preparing highly efficient nitrogen fertilizer Jiao, Gao-Jie; Peng, Pai; Sun, Shao-Long International Journal of Biological Macromolecules, Vol. 127 https://doi.org/10.1016/j.ijbiomac.2019.01.076	journal	April 2019
Modification of industrial softwood kraft lignin using Mannich reaction with and without phenolation pretreatment Du, Xueyu; Li, Jiebing; Lindström, Mikael E. Industrial Crops and Products, Vol. 52 https://doi.org/10.1016/j.indcrop.2013.11.035	journal	January 2014
Rigid polyurethane foams containing lignin oxyalkylated with ethylene carbonate and polyethylene glycol Zhang, Xuefeng; Kim, Yunsang; Elsayed, Islam Industrial Crops and Products, Vol. 141 https://doi.org/10.1016/j.indcrop.2019.111797	journal	December 2019
Effects of the advanced organosolv pretreatment strategies on structural properties of woody biomass Meng, Xianzhi; Bhagia, Samarthya; Wang, Yunxuan Industrial Crops and Products, Vol. 146 https://doi.org/10.1016/j.indcrop.2020.112144	journal	April 2020
A Mannich base biosorbent derived from alkaline lignin for lead removal from aqueous solution Ge, Yuanyuan; Song, Quanpeng; Li, Zhili Journal of Industrial and Engineering Chemistry, Vol. 23 https://doi.org/10.1016/j.jiec.2014.08.021	journal	March 2015
Organocatalytic synthesis of (poly)hydroxyurethanes from cyclic carbonates and amines Lambeth, Robert H.; Henderson, Terry J. Polymer, Vol. 54, Issue 21 https://doi.org/10.1016/j.polymer.2013.08.053	journal	October 2013
Green chemistry design in polymers derived from lignin: review and perspective Sternberg, James; Sequerth, Olivia; Pilla, Srikanth Progress in Polymer Science, Vol. 113 https://doi.org/10.1016/j.progpolymsci.2020.101344	journal	February 2021
Synthesis, characterization, and application of a bifunctional coupler containing a five- and a six-membered ring carbonate He, Yingchun; Keul, Helmut; Möller, Martin Reactive and Functional Polymers, Vol. 71, Issue 2 https://doi.org/10.1016/j.reactfunctpolym.2010.11.031	journal	February 2011
Synthesis of isosorbide based polyurethanes: An isocyanate free method Besse, Vincent; Auvergne, Rémi; Carlotti, Stéphane Reactive and Functional Polymers, Vol. 73, Issue 3 https://doi.org/10.1016/j.reactfunctpolym.2013.01.002	journal	March 2013
Hydroxyl-functionalized ionic liquid: a novel efficient catalyst for chemical fixation of CO₂ to cyclic carbonate Sun, Jian; Zhang, Suojiang; Cheng, Weiguo Tetrahedron Letters, Vol. 49, Issue 22, p. 3588-3591 https://doi.org/10.1016/j.tetlet.2008.04.022	journal	May 2008
Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective Upton, Brianna M.; Kasko, Andrea M. Chemical Reviews, Vol. 116, Issue 4, p. 2275-2306 https://doi.org/10.1021/acs.chemrev.5b00345	journal	December 2015
Biobased Amines: From Synthesis to Polymers; Present and Future Froidevaux, Vincent; Negrell, Claire; Caillol, Sylvain Chemical Reviews, Vol. 116, Issue 22 https://doi.org/10.1021/acs.chemrev.6b00486	journal	October 2016
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00588	journal	January 2018
Structural Characterization of Corn Stover Lignin after Hydrogen Peroxide Presoaking Prior to Ammonia Fiber Expansion Pretreatment Qiao, Xianliang; Zhao, Chao; Shao, Qianjun Energy & Fuels, Vol. 32, Issue 5 https://doi.org/10.1021/acs.energyfuels.8b00951	journal	April 2018
Synthesis of Polyurethanes Using Organocatalysis: A Perspective Sardon, Haritz; Pascual, Ana; Mecerreyes, David Macromolecules, Vol. 48, Issue 10 https://doi.org/10.1021/acs.macromol.5b00384	journal	May 2015
High Purity Limonene Dicarbonate as Versatile Building Block for Sustainable Non-Isocyanate Polyhydroxyurethane Thermosets and Thermoplastics Schimpf, Vitalij; Ritter, Benjamin S.; Weis, Philippe Macromolecules, Vol. 50, Issue 3 https://doi.org/10.1021/acs.macromol.6b02460	journal	January 2017
Segmented Thermoplastic Polymers Synthesized by Thiol–Ene Click Chemistry: Examples of Thiol–Norbornene and Thiol–Maleimide Click Reactions Jin, Kailong; Leitsch, Emily K.; Chen, Xi Macromolecules, Vol. 51, Issue 10 https://doi.org/10.1021/acs.macromol.8b00573	journal	May 2018
High-Performance Lignin-Containing Polyurethane Elastomers with Dynamic Covalent Polymer Networks Liu, Weifeng; Fang, Chang; Wang, Shengyu Macromolecules, Vol. 52, Issue 17 https://doi.org/10.1021/acs.macromol.9b01413	journal	August 2019
Hybrid Poly(hydroxy urethane)s: Folded-Sheet Morphology and Thermoreversible Adhesion Sukumaran Nair, Anitha; Cherian, Suchithra; Balachandran, Nisha ACS Omega, Vol. 4, Issue 8 https://doi.org/10.1021/acsomega.9b00789	journal	August 2019
Synthesis, Characterization, and Utilization of a Lignin-Based Adsorbent for Effective Removal of Azo Dye from Aqueous Solution Meng, Xianzhi; Scheidemantle, Brent; Li, Mi ACS Omega, Vol. 5, Issue 6 https://doi.org/10.1021/acsomega.9b03717	journal	February 2020
Synthesis and Characterization of Polyurethane Networks Derived from Soybean-Oil-Based Cyclic Carbonates and Bioderivable Diamines Samanta, Satyabrata; Selvakumar, Sermadurai; Bahr, James ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12 https://doi.org/10.1021/acssuschemeng.6b01409	journal	September 2016
Sustainable and Antioxidant Lignin–Polyester Copolymers and Nanofibers for Potential Healthcare Applications Kai, Dan; Zhang, Kangyi; Jiang, Lu ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 7 https://doi.org/10.1021/acssuschemeng.7b00850	journal	June 2017
Chemical Transformations of Poplar Lignin during Cosolvent Enhanced Lignocellulosic Fractionation Process Meng, Xianzhi; Parikh, Aakash; Seemala, Bhogeswararao ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 7 https://doi.org/10.1021/acssuschemeng.8b01028	journal	May 2018
Biobased Polyurethane Coatings with High Biomass Content: Tailored Properties by Lignin Selection de Haro, Juan Carlos; Allegretti, Chiara; Smit, Arjan T. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 13 https://doi.org/10.1021/acssuschemeng.9b01873	journal	June 2019
On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-isocyanate Polyurethane Delebecq, Etienne; Pascault, Jean-Pierre; Boutevin, Bernard Chemical Reviews, Vol. 113, Issue 1 https://doi.org/10.1021/cr300195n	journal	October 2012
Aliphatic Poly(urethane−amine)s Synthesized by Copolymerization of Aziridines and Supercritical Carbon Dioxide Ihata, Osamu; Kayaki, Yoshihito; Ikariya, Takao Macromolecules, Vol. 38, Issue 15 https://doi.org/10.1021/ma050549o	journal	June 2005
Cyclic Carbonate Formation from Carbon Dioxide and Oxiranes in Tetrabutylammonium Halides as Solvents and Catalysts Caló, Vincenzo; Nacci, Angelo; Monopoli, Antonio Organic Letters, Vol. 4, Issue 15 https://doi.org/10.1021/ol026189w	journal	July 2002
Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy Meng, Xianzhi; Crestini, Claudia; Ben, Haoxi Nature Protocols, Vol. 14, Issue 9 https://doi.org/10.1038/s41596-019-0191-1	journal	August 2019
Preparation of lignin/glycerol-based bis(cyclic carbonate) for the synthesis of polyurethanes Chen, Qin; Gao, Keke; Peng, Chang Green Chemistry, Vol. 17, Issue 9 https://doi.org/10.1039/C5GC01340B	journal	January 2015
Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: an environmentally friendly approach Chatterjee, Maya; Ishizaka, Takayuki; Kawanami, Hajime Green Chemistry, Vol. 18, Issue 2 https://doi.org/10.1039/C5GC01352F	journal	January 2016
The strong association of condensed phenolic moieties in isolated lignins with their inhibition of enzymatic hydrolysis Sun, Shaolong; Huang, Yang; Sun, Runcang Green Chemistry, Vol. 18, Issue 15 https://doi.org/10.1039/C6GC00685J	journal	January 2016
Chemical modifications of lignin for the preparation of macromers containing cyclic carbonates Salanti, Anika; Zoia, Luca; Orlandi, Marco Green Chemistry, Vol. 18, Issue 14 https://doi.org/10.1039/C6GC01028H	journal	January 2016
Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis Yoo, Chang Geun; Li, Mi; Meng, Xianzhi Green Chemistry, Vol. 19, Issue 8 https://doi.org/10.1039/C6GC03627A	journal	January 2017
Polyurethane types, synthesis and applications – a review Akindoyo, John O.; Beg, M. D. H.; Ghazali, Suriati RSC Advances, Vol. 6, Issue 115 https://doi.org/10.1039/C6RA14525F	journal	January 2016
Lignin transformations for high value applications: towards targeted modifications using green chemistry Gillet, S.; Aguedo, M.; Petitjean, L. Green Chemistry, Vol. 19, Issue 18 https://doi.org/10.1039/C7GC01479A	journal	January 2017
Utilization of cyclocarbonated lignin as a bio-based cross-linker for the preparation of poly(hydroxy urethane)s Salanti, Anika; Zoia, Luca; Mauri, Michele RSC Advances, Vol. 7, Issue 40 https://doi.org/10.1039/C7RA03416D	journal	January 2017
Diol pretreatment to fractionate a reactive lignin in lignocellulosic biomass biorefineries Dong, Chengyu; Meng, Xianzhi; Yeung, Chi Shun Green Chemistry, Vol. 21, Issue 10 https://doi.org/10.1039/C9GC00596J	journal	January 2019
Are lignin-derived carbon fibers graphitic enough? Sagues, William J.; Jain, Ankush; Brown, Dylan Green Chemistry, Vol. 21, Issue 16 https://doi.org/10.1039/C9GC01806A	journal	January 2019
Waterborne isocyanate-free polyurethane epoxy hybrid coatings synthesized from sustainable fatty acid diamine Zhang, Cheng; Wang, Haoran; Zhou, Qixin Green Chemistry, Vol. 22, Issue 4 https://doi.org/10.1039/C9GC03335A	journal	January 2020
Research status, industrial application demand and prospects of phenolic resin Xu, Yanru; Guo, Lifang; Zhang, Haonan RSC Advances, Vol. 9, Issue 50 https://doi.org/10.1039/C9RA06487G	journal	January 2019
Materials for the biorefinery: high bio-content, shape memory Kraft lignin-derived non-isocyanate polyurethane foams using a non-toxic protocol Sternberg, James; Pilla, Srikanth Green Chemistry, Vol. 22, Issue 20 https://doi.org/10.1039/D0GC01659D	journal	January 2020
Probing catalytic activity of halide salts by electrical conductivity in the coupling reaction of CO2 and propylene oxide Guo, Liping; Wang, Congmin; Luo, Xiaoyan Chemical Communications, Vol. 46, Issue 32 https://doi.org/10.1039/c0cc00584c	journal	January 2010
Cyclic limonene dicarbonate as a new monomer for non-isocyanate oligo- and polyurethanes (NIPU) based upon terpenes Bähr, Moritz; Bitto, Alexandro; Mülhaupt, Rolf Green Chemistry, Vol. 14, Issue 5 https://doi.org/10.1039/c2gc35099h	journal	January 2012
Glycerol-, pentaerythritol- and trimethylolpropane-based polyurethanes and their cellulose carbonate composites prepared via the non-isocyanate route with catalytic carbon dioxide fixation Fleischer, Maria; Blattmann, Hannes; Mülhaupt, Rolf Green Chemistry, Vol. 15, Issue 4 https://doi.org/10.1039/c3gc00078h	journal	January 2013
High activity and switchable selectivity in the synthesis of cyclic and polymeric cyclohexene carbonates with iron amino triphenolate catalysts Taherimehr, Masoumeh; Al-Amsyar, Syed M.; Whiteoak, Christopher J. Green Chemistry, Vol. 15, Issue 11 https://doi.org/10.1039/c3gc41303a	journal	January 2013
Development of lignin-based polyurethane thermoplastics Saito, Tomonori; Perkins, Joshua H.; Jackson, Daniel C. RSC Advances, Vol. 3, Issue 44, p. 21832-21840 https://doi.org/10.1039/c3ra44794d	journal	January 2013
Ultrasonic-assisted synthesis of aminated lignin by a Mannich reaction and its decolorizing properties for anionic azo-dyes Wang, Xiaohong; Zhang, Yike; Hao, Chen RSC Advances, Vol. 4, Issue 53 https://doi.org/10.1039/c4ra03133d	journal	January 2014
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Co-curing of epoxy resins with aminated lignins: insights into the role of lignin homo crosslinking during lignin amination on the elastic properties Ott, Marcus W.; Dietz, Christian; Trosien, Simon Holzforschung, Vol. 75, Issue 4 https://doi.org/10.1515/hf-2020-0060	journal	August 2020
Bio-based polyurethane prepared from Kraft lignin and modified castor oil Tavares, L. B.; Boas, C. V.; Schleder, G. R. Express Polymer Letters, Vol. 10, Issue 11 https://doi.org/10.3144/expresspolymlett.2016.86	journal	January 2016
Synthesis and Properties of Waterborne Polyurethane (WBPU)/Modified Lignin Amine (MLA) Adhesive: A Promising Adhesive Material Rahman, Mohammad; Zahir, Md.; Kim, Han Polymers, Vol. 8, Issue 9 https://doi.org/10.3390/polym8090318	journal	August 2016

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54 ENVIRONMENTAL SCIENCES
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Title: Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

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