Catalytic conversion of high S-lignin to a sustainable tri-epoxide polymer precursor

Liu, Baoyuan; Sanchez, Melissa; Truong, Julianne; Ford, Peter C.; Abu-Omar, Mahdi M.

doi:10.1039/d2gc01278b

Title: Catalytic conversion of high S-lignin to a sustainable tri-epoxide polymer precursor

Journal Article · 01 January 2022 · Green Chemistry

DOI: https://doi.org/10.1039/d2gc01278b · OSTI ID:1978898

Liu, Baoyuan ^[1]; Sanchez, Melissa ^[2]; Truong, Julianne ^[3];

^[2];

^[2]

Univ. of California, Santa Barbara, CA (United States); OSTI
Univ. of California, Santa Barbara, CA (United States)
Department of Chemistry & Biochemistry, University of California, Santa Barbara, Building 232, Santa Barbara, California, 93106-9510, USA

More than 40 million tons of thermosetting plastics are produced annually and 70% of those are epoxy polymers. The synthesis of bio-based epoxide provides a pathway for making renewable thermoset plastics. We describe in this study the use of a genetically modified high-S poplar lignin to produce 4-propyl-2,6-dimethoxyphenol (DMPP), which is converted to the tri-functional compound propylpyrogallol (DMPPO) by a reaction catalysed by N₂O₅ in the green solvent water. The resulting DMPPO can be converted to a novel tri-epoxide by reaction with epichlorohydrin. Native high-S lignin as well as several organosolv lignins extracted from this poplar biomass were investigated as feedstocks. Notably, direct reductive catalytic fractionation (RCF) of the high-S poplar wood over Pd–Zn/C catalyst with Pd : Zn ratio 1 : 10 at 225 °C under 35 bar H₂ in methanol gave the highest yield of biophenol monomers from the lignin present, the major product being DMPP. Under optimized conditions, conversion of DMPP to DMPPO over the Nb₂O₅ was nearly quantitative (96% yield), and this conversion could be made without extensive prior purification of the DMPP. The Nb₂O₅ catalyst could be recycled several times before significant deactivation. This sequence of two catalytic reactions demonstrates that the production of epoxides from lignin-derived DMPPO is a realistic strategy for making renewable polymer building blocks from biomass.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0019161

OSTI ID:: 1978898

Journal Information:: Green Chemistry, Journal Name: Green Chemistry Journal Issue: 12 Vol. 24; ISSN GRCHFJ; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

A New Class of Renewable Thermoplastics with Extraordinary Performance from Nanostructured Lignin-Elastomers Tran, Chau D.; Chen, Jihua; Keum, Jong K. Advanced Functional Materials, Vol. 26, Issue 16, p. 2677-2685 https://doi.org/10.1002/adfm.201504990	journal	March 2016
Catalytic Scissoring of Lignin into Aryl Monomers Wang, Min; Wang, Feng Advanced Materials, Vol. 31, Issue 50 https://doi.org/10.1002/adma.201901866	journal	July 2019
Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T. Angewandte Chemie International Edition, Vol. 55, Issue 29 https://doi.org/10.1002/anie.201510351	journal	June 2016
Recent advances in low-cost carbon fiber manufacture from lignin Baker, Darren A.; Rials, Timothy G. Journal of Applied Polymer Science, Vol. 130, Issue 2 https://doi.org/10.1002/app.39273	journal	April 2013
Lignin as Renewable Raw Material Calvo-Flores, Francisco García; Dobado, José A. ChemSusChem, Vol. 3, Issue 11 https://doi.org/10.1002/cssc.201000157	journal	September 2010
Synthesis of bio-based epoxy resin from gallic acid with various epoxy equivalent weights and its effects on coating properties Patil, Deepak M.; Phalak, Ganesh A.; Mhaske, S. T. Journal of Coatings Technology and Research, Vol. 14, Issue 2 https://doi.org/10.1007/s11998-016-9853-x	journal	November 2016
Chemicals From Lignin Luo, Hao; Abu-Omar, Mahdi M. Encyclopedia of Sustainable Technologies https://doi.org/10.1016/B978-0-12-409548-9.10235-0	book	January 2017
Opportunities and challenges in biological lignin valorization Beckham, Gregg T.; Johnson, Christopher W.; Karp, Eric M. Current Opinion in Biotechnology, Vol. 42 https://doi.org/10.1016/j.copbio.2016.02.030	journal	December 2016
Production of hydrocarbon fuels from heavy fraction of bio-oil through hydrodeoxygenative upgrading with Ru-based catalyst Zhang, Xinghua; Tang, Wenwu; Zhang, Qi Fuel, Vol. 215 https://doi.org/10.1016/j.fuel.2017.11.111	journal	March 2018
Relationship of thermal degradation behavior and chemical structure of lignin isolated from palm kernel shell under different process severities Ma, Zhongqing; Wang, Junhao; Zhou, Hanzhi Fuel Processing Technology, Vol. 181 https://doi.org/10.1016/j.fuproc.2018.09.020	journal	December 2018
Lignin as a base material for materials applications: Chemistry, application and economics Stewart, Derek Industrial Crops and Products, Vol. 27, Issue 2 https://doi.org/10.1016/j.indcrop.2007.07.008	journal	March 2008
A concise review of current lignin production, applications, products and their environmental impact Bajwa, D. S.; Pourhashem, G.; Ullah, A. H. Industrial Crops and Products, Vol. 139 https://doi.org/10.1016/j.indcrop.2019.111526	journal	November 2019
Sequential transformation and utilization of natural network polymer “LIGNIN” Funaoka, Masamitsu Reactive and Functional Polymers, Vol. 73, Issue 2 https://doi.org/10.1016/j.reactfunctpolym.2012.05.010	journal	February 2013
A review on lignin-based polymeric, micro- and nano-structured materials Duval, Antoine; Lawoko, Martin Reactive and Functional Polymers, Vol. 85 https://doi.org/10.1016/j.reactfunctpolym.2014.09.017	journal	December 2014
Biobased Epoxy Nanocomposites Derived from Lignin-Based Monomers Zhao, Shou; Abu-Omar, Mahdi M. Biomacromolecules, Vol. 16, Issue 7 https://doi.org/10.1021/acs.biomac.5b00670	journal	June 2015
Renewable Thermoplastics Based on Lignin-Derived Polyphenols Zhao, Shou; Abu-Omar, Mahdi M. Macromolecules, Vol. 50, Issue 9 https://doi.org/10.1021/acs.macromol.7b00064	journal	April 2017
Catechol-Mediated Glycidylation toward Epoxy Vitrimers/Polymers with Tunable Properties Zhao, Shou; Abu-Omar, Mahdi M. Macromolecules, Vol. 52, Issue 10 https://doi.org/10.1021/acs.macromol.9b00334	journal	May 2019
Mechanical and Morphological Properties of Lignin-Based Thermosets Jawerth, Marcus E.; Brett, Calvin J.; Terrier, Cédric ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b01007	journal	January 2020
Fragmentation of Lignin Samples with Commercial Pd/C under Ambient Pressure of Hydrogen Gao, Fang; Webb, Jonathan D.; Sorek, Hagit ACS Catalysis, Vol. 6, Issue 11 https://doi.org/10.1021/acscatal.6b02028	journal	October 2016
Characterization of Organosolv Birch Lignins: Toward Application-Specific Lignin Production Paulsen Thoresen, Petter; Lange, Heiko; Crestini, Claudia ACS Omega, Vol. 6, Issue 6 https://doi.org/10.1021/acsomega.0c05719	journal	February 2021
Organosolv Fractionation of Walnut Shell Biomass to Isolate Lignocellulosic Components for Chemical Upgrading of Lignin to Aromatics Nishide, Rebecca N.; Truong, Julianne H.; Abu-Omar, Mahdi M. ACS Omega, Vol. 6, Issue 12 https://doi.org/10.1021/acsomega.0c05936	journal	March 2021
Nonprecious Metal/Bimetallic Catalytic Hydrogenolysis of Lignin in a Mixed-Solvent System Cheng, Chongbo; Li, Pengfei; Yu, Wenbing ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 43 https://doi.org/10.1021/acssuschemeng.0c05362	journal	October 2020
Case Study in Kraft Lignin Fractionation: “Structurally Purified” Lignin Fractions—The Role of Solvent H-Bonding Affinity Ebrahimi Majdar, Reza; Ghasemian, Ali; Resalati, Hossein ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 45 https://doi.org/10.1021/acssuschemeng.0c05364	journal	November 2020
Molecular Lignin Solubility and Structure in Organic Solvents Vermaas, Josh V.; Crowley, Michael F.; Beckham, Gregg T. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 48 https://doi.org/10.1021/acssuschemeng.0c07156	journal	November 2020
Oxidative Catalytic Fractionation and Depolymerization of Lignin in a One-Pot Single-Catalyst System Du, Xu; Tricker, Andrew W.; Yang, Weisheng ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 23 https://doi.org/10.1021/acssuschemeng.0c08448	journal	May 2021
Renewable Epoxy Networks Derived from Lignin-Based Monomers: Effect of Cross-Linking Density Zhao, Shou; Abu-Omar, Mahdi M. ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 11 https://doi.org/10.1021/acssuschemeng.6b01446	journal	July 2016
Fractionation of Organosolv Lignin Using Acetone:Water and Properties of the Obtained Fractions Sadeghifar, Hasan; Wells, Tyrone; Le, Rosemary Khuu ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 1 https://doi.org/10.1021/acssuschemeng.6b01955	journal	November 2016
Hydrogenolysis of Organosolv Lignin in Ethanol/Isopropanol Media without Added Transition-Metal Catalyst Cheng, Chongbo; Truong, Julianne; Barrett, Jacob A. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 2 https://doi.org/10.1021/acssuschemeng.9b05820	journal	December 2019
Mild Organosolv Lignin Extraction with Alcohols: The Importance of Benzylic Alkoxylation Zijlstra, Douwe S.; Lahive, Ciaran W.; Analbers, Coen A. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 13 https://doi.org/10.1021/acssuschemeng.9b07222	journal	March 2020
Multiphase materials with lignin. 11. Starlike copolymers with caprolactone de Oliveira, Willer; Glasser, Wolfgang G. Macromolecules, Vol. 27, Issue 1 https://doi.org/10.1021/ma00079a002	journal	January 1994
Tuning the lignin oil OH-content with Ru and Pd catalysts during lignin hydrogenolysis on birch wood Van den Bosch, S.; Schutyser, W.; Koelewijn, S. -F. Chemical Communications, Vol. 51, Issue 67 https://doi.org/10.1039/C5CC04025F	journal	January 2015
Mapping reactivities of aromatic models with a lignin disassembly catalyst. Steps toward controlling product selectivity Bernt, Christopher M.; Bottari, Giovanni; Barrett, Jacob A. Catalysis Science & Technology, Vol. 6, Issue 9 https://doi.org/10.1039/C5CY01555C	journal	January 2016
Mechanistic investigation of the Zn/Pd/C catalyzed cleavage and hydrodeoxygenation of lignin Klein, Ian; Marcum, Christopher; Kenttämaa, Hilkka Green Chemistry, Vol. 18, Issue 8 https://doi.org/10.1039/C5GC01325A	journal	January 2016
An approach towards tailoring interfacial structures and properties of multiphase renewable thermoplastics from lignin–nitrile rubber Bova, Tony; Tran, Chau D.; Balakshin, Mikhail Y. Green Chemistry, Vol. 18, Issue 20 https://doi.org/10.1039/C6GC01067A	journal	January 2016
Tuning Ni nanoparticles and the acid sites of silica-alumina for liquefaction and hydrodeoxygenation of lignin to cyclic alkanes Kong, Jiechen; Li, Bolong; Zhao, Chen RSC Advances, Vol. 6, Issue 76 https://doi.org/10.1039/C6RA16977E	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
Towards high-yield lignin monomer production Shuai, Li; Saha, Basudeb Green Chemistry, Vol. 19, Issue 16 https://doi.org/10.1039/C7GC01676J	journal	January 2017
Lignin extraction and catalytic upgrading from genetically modified poplar Luo, Hao; Abu-Omar, Mahdi M. Green Chemistry, Vol. 20, Issue 3 https://doi.org/10.1039/C7GC03417B	journal	January 2018
State-of-the-art catalytic hydrogenolysis of lignin for the production of aromatic chemicals Cheng, Chongbo; Shen, Dekui; Gu, Sai Catalysis Science & Technology, Vol. 8, Issue 24 https://doi.org/10.1039/C8CY00845K	journal	January 2018
One-pot hydrodeoxygenation (HDO) of lignin monomers to C9 hydrocarbons co-catalysed by Ru/C and Nb ₂ O ₅ Li, Simin; Liu, Baoyuan; Truong, Julianne Green Chemistry, Vol. 22, Issue 21 https://doi.org/10.1039/D0GC01692F	journal	January 2020
Are lignin-derived monomers and polymers truly sustainable? An in-depth green metrics calculations approach Fadlallah, Sami; Sinha Roy, Pallabi; Garnier, Gil Green Chemistry, Vol. 23, Issue 4 https://doi.org/10.1039/D0GC03982A	journal	January 2021
Sustainable alternative to bisphenol A epoxy resin: high-performance recyclable epoxy vitrimers derived from protocatechuic acid Tao, Yangqing; Fang, Linxuan; Dai, Menglu Polymer Chemistry, Vol. 11, Issue 27 https://doi.org/10.1039/D0PY00545B	journal	January 2020
Catalytic disassembly of an organosolv lignin via hydrogen transfer from supercritical methanol Barta, Katalin; Matson, Theodore D.; Fettig, Makayla L. Green Chemistry, Vol. 12, Issue 9 https://doi.org/10.1039/c0gc00181c	journal	January 2010
Modified lignin in tobacco and poplar plants over-expressing the Arabidopsis gene encoding ferulate 5-hydroxylase Franke, Rochus; McMichael, Colleen M.; Meyer, Knut The Plant Journal, Vol. 22, Issue 3, p. 223-234 https://doi.org/10.1046/j.1365-313x.2000.00727.x	journal	May 2000
Bisphenol A: Food Exposure and Impact on Human Health: Bisphenol A and human health effect… Almeida, Susana; Raposo, António; Almeida-González, Maira Comprehensive Reviews in Food Science and Food Safety, Vol. 17, Issue 6 https://doi.org/10.1111/1541-4337.12388	journal	September 2018
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M. Science, Vol. 354, Issue 6310 https://doi.org/10.1126/science.aaf7810	journal	October 2016
Lignin as a Renewable Resource of Hydrocarbon Products and Energy Carriers (A Review) Arapova, O. V.; Chistyakov, A. V.; Tsodikov, M. V. Petroleum Chemistry, Vol. 60, Issue 3 https://doi.org/10.1134/S0965544120030044	journal	March 2020
2016 Billion-Ton Report: Advancing Domestic Resources for a Thriving Bioeconomy Langholtz, M. H.; Stokes, B. J.; Eaton, L. M. https://doi.org/10.2172/1271651 DOE/EE-1440	report	July 2016
Organosolv Fractionation of Softwood Biomass for Biofuel and Biorefinery Applications Nitsos, Christos; Rova, Ulrika; Christakopoulos, Paul Energies, Vol. 11, Issue 1, p. 50 https://doi.org/10.3390/en11010050	journal	December 2017

Similar Records

Multi-functional syringol based epoxides and properties of their thermoset polymers

Journal Article · 2024 · RSC Sustainability · OSTI ID:2429346

Sanchez, Melissa; Ford, Peter C.; Abu-Omar, Mahdi M.

One-pot hydrodeoxygenation (HDO) of lignin monomers to C9 hydrocarbons co-catalysed by Ru/C and Nb₂O₅

Journal Article · 2020 · Green Chemistry · OSTI ID:1852899

Li, Simin; Liu, Baoyuan; Truong, Julianne; +3 more

Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis

Journal Article · 2017 · Green Chemistry · OSTI ID:1352795

Yoo, Chang Geun; Li, Mi; Meng, Xianzhi; +2 more

Related Subjects

09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Science & Technology - Other Topics

Title: Catalytic conversion of high S-lignin to a sustainable tri-epoxide polymer precursor

Citation Formats

References (49)

Similar Records

Related Subjects