Synthesis of Bio-Based Repairable Polyimines with Tailored Properties by Lignin Fractionation

Xie, Di; Pu, Yunqiao (Joseph); Bryant, Nathan D.; Harper, David P.; Wang, Wei; Ragauskas, Arthur J.; Li, Mi

doi:10.1021/acssuschemeng.3c08482

Title: Synthesis of Bio-Based Repairable Polyimines with Tailored Properties by Lignin Fractionation

Journal Article · 11 April 2024 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.3c08482 · OSTI ID:2447262

Xie, Di ^[1];

^[2]; Bryant, Nathan D. ^[3];

^[1];

^[4];

^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS); Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS)

Developing sustainable polymers with low-value lignin remains a challenge. Herein, lignin-containing repairable polyimines were synthesized with tailored properties using lignin fractionation. First, softwood Kraft lignin is fractionated into a more homogeneous fraction with a lower molecular weight and a higher OH content. Next, Kraft lignin and its fraction are esterified by levulinic acid to introduce active ketone groups and subsequently condensed with oleylamine (OAm) and bis(3-aminopropyl)-terminated polydimethylsiloxane (PDMS) via a catalyst-free Schiff-base reaction to form grafted lignin-OAm copolymers and cross-linked lignin-PDMS polymer networks (MKL-P and MFL-P), respectively. Results show that lignin-OAm polyimines can be self-repaired and hot reprocessed under pressure, while lignin-PDMS polyimines can be repaired with the assistance of a healing agent, heat, and pressure. Dynamic mechanical analyses demonstrate that the stress–relaxation behaviors of the polyimines follow the Arrhenius law under thermal-stress activation, indicating the occurrence of transimination. Moreover, compared with Kraft lignin, the lignin fraction ameliorates the grafting density of ketones and enhances the cross-linking density of lignin-PDMS polyimine networks. The higher cross-linking density of MFL-P leads to superior stress–relaxation activation energy, thermal stability, hydrophobicity, and light-shielding ability but inferior repairability and translucency. Finally, this work provides insights into the polymerization of lignin-based polymer networks and the potential application of lignin-PDMS polyimines for repairable, translucent, anti-UV, and hydrophobic coatings.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2447262

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 17 Vol. 12; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

In Situ Lignin Modification toward Photonic Wood Xia, Qinqin; Chen, Chaoji; Yao, Yonggang Advanced Materials, Vol. 33, Issue 8 https://doi.org/10.1002/adma.202001588	journal	January 2021
Closed‐Loop Recycling of Poly(Imine‐Carbonate) Derived from Plastic Waste and Bio‐based Resources Saito, Keita; Eisenreich, Fabian; Türel, Tankut Angewandte Chemie International Edition, Vol. 61, Issue 43 https://doi.org/10.1002/anie.202211806	journal	September 2022
Thermal stability and degradation of biological terpolyesters over a broad temperature range Tanadchangsaeng, Nuttapol; Yu, Jian Journal of Applied Polymer Science, Vol. 132, Issue 13 https://doi.org/10.1002/app.41715	journal	December 2014
A High‐Lignin‐Content, Removable, and Glycol‐Assisted Repairable Coating Based on Dynamic Covalent Bonds Hao, Cheng; Liu, Tuan; Zhang, Shuai ChemSusChem, Vol. 12, Issue 5 https://doi.org/10.1002/cssc.201802615	journal	February 2019
Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis Duval, Antoine; Layrac, Géraldine; Zomeren, André ChemSusChem, Vol. 14, Issue 1 https://doi.org/10.1002/cssc.202001976	journal	October 2020
Recyclable Carbon Fiber Reinforced Vanillin‐Based Polyimine Vitrimers: Degradation and Mechanical Properties Study Wang, Yuli; Xu, Anchang; Zhang, Lingwei Macromolecular Materials and Engineering, Vol. 307, Issue 7 https://doi.org/10.1002/mame.202100893	journal	April 2022
Kraft lignin fractionation by organic solvents: Correlation between molar mass and higher heating value Araújo, Luísa Carvalho Pereira; Yamaji, Fábio Minoru; Lima, Vitor Hugo Bioresource Technology, Vol. 314 https://doi.org/10.1016/j.biortech.2020.123757 123757	journal	September 2020
Lignin-based benzoxazines: A tunable key-precursor for the design of hydrophobic coatings, fire resistant materials and catalyst-free vitrimers Adjaoud, Antoine; Puchot, Laura; Federico, Carlos Eloy Chemical Engineering Journal, Vol. 453 https://doi.org/10.1016/j.cej.2022.139895	journal	February 2023
Lignin-derivatives based polymers, blends and composites: A review Naseem, Amina; Tabasum, Shazia; Zia, Khalid Mahmood International Journal of Biological Macromolecules, Vol. 93 https://doi.org/10.1016/j.ijbiomac.2016.08.030	journal	December 2016
Solvent-free synthesis of high-performance polyurethane elastomer based on low-molecular-weight alkali lignin Huang, Jianhua; Wang, Haixu; Liu, Weifeng International Journal of Biological Macromolecules, Vol. 225 https://doi.org/10.1016/j.ijbiomac.2022.11.207	journal	January 2023
Esterification of lignin with long chain fatty acids for the stabilization of oil-in-water Pickering emulsions Shorey, Rohan; Mekonnen, Tizazu H. International Journal of Biological Macromolecules, Vol. 230 https://doi.org/10.1016/j.ijbiomac.2023.123143	journal	March 2023
Reduced nutrient release and greenhouse gas emissions of lignin-based coated urea by synergy of carbon black and polysiloxane Chen, Xiaojuan; Guo, Tao; Mo, Xiao International Journal of Biological Macromolecules, Vol. 231 https://doi.org/10.1016/j.ijbiomac.2023.123334	journal	March 2023
Influence of structure and functional group of modified kraft lignin on adsorption behavior of dye Song, Changyong; Gao, Chao; Fatehi, Pedram International Journal of Biological Macromolecules, Vol. 240 https://doi.org/10.1016/j.ijbiomac.2023.124368	journal	June 2023
Softwood kraft lignin: Raw material for the future Gellerstedt, Göran Industrial Crops and Products, Vol. 77 https://doi.org/10.1016/j.indcrop.2015.09.040	journal	December 2015
Preparation of a novel lignin-based film with high solid content and its physicochemical characteristics Chen, Xiaojuan; Li, Zhonghua; Zhang, Lidan Industrial Crops and Products, Vol. 164 https://doi.org/10.1016/j.indcrop.2021.113396	journal	June 2021
Revealing the structure-activity relationship between lignin and anti-UV radiation Lin, Minsheng; Yang, Linjie; Zhang, Han Industrial Crops and Products, Vol. 174 https://doi.org/10.1016/j.indcrop.2021.114212	journal	December 2021
A review on recent approaches to sustainable bio-based epoxy vitrimer from epoxidized vegetable oils Chong, K. L.; Lai, J. C.; Rahman, R. A. Industrial Crops and Products, Vol. 189 https://doi.org/10.1016/j.indcrop.2022.115857	journal	December 2022
Efficient transformation of renewable vanillin into reprocessable, acid-degradable and flame retardant polyimide vitrimers Yang, Xiangyu; Ke, Yanzi; Chen, Qian Journal of Cleaner Production, Vol. 333 https://doi.org/10.1016/j.jclepro.2021.130043	journal	January 2022
Synthesis and Characterization of Lignin-grafted-poly(ε-caprolactone) from Different Biomass Sources Li, Mi; Pu, Yunqiao; Chen, Fang New Biotechnology, Vol. 60 https://doi.org/10.1016/j.nbt.2020.10.005	journal	January 2021
Deconvolution of the segmental and chain modes in amorphous polymers: Do the short-chain modes affect the bulk relaxation? Grassia, Luigi; D'Amore, Alberto Polymer, Vol. 225 https://doi.org/10.1016/j.polymer.2021.123801	journal	May 2021
Biological Activities and Emerging Roles of Lignin and Lignin-Based Products─A Review Shu, Fan; Jiang, Bo; Yuan, Yufeng Biomacromolecules, Vol. 22, Issue 12 https://doi.org/10.1021/acs.biomac.1c00805	journal	November 2021
Dynamic Covalent Polymer Networks: A Molecular Platform for Designing Functions beyond Chemical Recycling and Self-Healing Zheng, Ning; Xu, Yang; Zhao, Qian Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00938	journal	January 2021
Facile Preparation of Polyimine Vitrimers with Enhanced Creep Resistance and Thermal and Mechanical Properties via Metal Coordination Wang, Sheng; Ma, Songqi; Li, Qiong Macromolecules, Vol. 53, Issue 8 https://doi.org/10.1021/acs.macromol.0c00036	journal	April 2020
Dynamic Covalent Polymer Networks Based on Degenerative Imine Bond Exchange: Tuning the Malleability and Self-Healing Properties by Solvent Chao, Albert; Negulescu, Ioan; Zhang, Donghui Macromolecules, Vol. 49, Issue 17 https://doi.org/10.1021/acs.macromol.6b01443	journal	August 2016
Stress Relaxation in Epoxy Thermosets via a Ferrocene-Based Amine Curing Agent Jones, Brad H.; Wheeler, David R.; Black, Hayden T. Macromolecules, Vol. 50, Issue 13 https://doi.org/10.1021/acs.macromol.7b00501	journal	June 2017
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
Reprocessable Cross-Linked Polymer Networks: Are Associative Exchange Mechanisms Desirable? Elling, Benjamin R.; Dichtel, William R. ACS Central Science, Vol. 6, Issue 9 https://doi.org/10.1021/acscentsci.0c00567	journal	July 2020
Effect of the Lignin Structure on the Physicochemical Properties of Lignin-Grafted-Poly(ε-caprolactone) and Its Application for Water/Oil Separation Xie, Di; Pu, Yunqiao; Meng, Xianzhi ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 50, p. 16882-16895 https://doi.org/10.1021/acssuschemeng.2c05495	journal	December 2022
Polyurethane Coatings Based on Chemically Unmodified Fractionated Lignin Griffini, Gianmarco; Passoni, Valeria; Suriano, Raffaella ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 6 https://doi.org/10.1021/acssuschemeng.5b00073	journal	April 2015
Lignin Functionalized with Succinic Anhydride as Building Block for Biobased Thermosetting Polyester Coatings Scarica, Carmela; Suriano, Raffaella; Levi, Marinella ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 3 https://doi.org/10.1021/acssuschemeng.7b03583	journal	January 2018
Fast Fractionation of Technical Lignins by Organic Cosolvents Wang, Yun-Yan; Li, Mi; Wyman, Charles E. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 5 https://doi.org/10.1021/acssuschemeng.7b04546	journal	March 2018
Vanillin-Based Polyschiff Vitrimers: Reprocessability and Chemical Recyclability Geng, Hongwei; Wang, Yuli; Yu, Qingqing ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b03925	journal	September 2018
High Performance Thermoplastic Elastomers with Biomass Lignin as Plastic Phase Huang, Jinhao; Liu, Weifeng; Qiu, Xueqing ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 7 https://doi.org/10.1021/acssuschemeng.8b04936	journal	February 2019
Oleylamine in Nanoparticle Synthesis Mourdikoudis, Stefanos; Liz-Marzán, Luis M. Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm4000476	journal	February 2013
Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets Scheutz, Georg M.; Lessard, Jacob J.; Sims, Michael B. Journal of the American Chemical Society, Vol. 141, Issue 41 https://doi.org/10.1021/jacs.9b07922	journal	September 2019
Closed-loop recycling of polyethylene-like materials Häußler, Manuel; Eck, Marcel; Rothauer, Dario Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-020-03149-9	journal	February 2021
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
Re-healable polyimine thermosets: polymer composition and moisture sensitivity Taynton, Philip; Zhu, Chengpu; Loob, Samuel Polymer Chemistry, Vol. 7, Issue 46 https://doi.org/10.1039/C6PY01395C	journal	January 2016
Sustainable valorization of lignin with levulinic acid and its application in polyimine thermosets Huang, Kaifeng; Ma, Songqi; Wang, Sheng Green Chemistry, Vol. 21, Issue 18 https://doi.org/10.1039/C9GC02384D	journal	January 2019
Dynamic imine chemistry Belowich, Matthew E.; Stoddart, J. Fraser Chemical Society Reviews, Vol. 41, Issue 6 https://doi.org/10.1039/c2cs15305j	journal	January 2012
Molecular weight effects on the stress-relaxation behavior of soft thermoplastic elastomer by means of temperature scanning stress relaxation (TSSR) Sbrescia, Simone; Engels, Tom; Van Ruymbeke, Evelyne Journal of Rheology, Vol. 66, Issue 6 https://doi.org/10.1122/8.0000444	journal	November 2022
A novel and highly efficient polymerization of sulfomethylated alkaline lignins via alkyl chain cross-linking method Hong, Nanlong; Yu, Wei; Xue, Yuyuan Holzforschung, Vol. 70, Issue 4 https://doi.org/10.1515/hf-2015-0043	journal	August 2015

Similar Records

Aqueous-Based Polyimine Functionalization of Cellulose Nanofibrils for Effective Drying and Polymer Composite Reinforcement

Journal Article · 2022 · ACS Applied Polymer Materials · OSTI ID:1892402

Lamm, Meghan E.; Li, Kai; Copenhaver, Katie; +5 more

Rotational dynamics of naphthalene-labeled cross-link junctions in poly(dimethylsiloxane) elastomers

Journal Article · 1996 · Journal of Physical Chemistry · OSTI ID:249660

Leezenberg, P B; Marcus, A H; Frank, C W; +1 more

Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation

Journal Article · 2019 · ACS Applied Polymer Materials · OSTI ID:1545197

Wang, Yun-Yan; Wyman, Charles E.; Cai, Charles M.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cross-linking polymer network
dynamic imine bond
lignin
polyimines
repairability

Title: Synthesis of Bio-Based Repairable Polyimines with Tailored Properties by Lignin Fractionation

Citation Formats

References (42)

Similar Records

Related Subjects