[en] Ethylene brassylate is a renewable macrolactone from castor oil that can be polymerized via ring-opening polymerization (ROP) to obtain a fully biosourced biodegradable polyester. ROP mediated by organometallic catalysts leads to high molar mass poly(ethylene brassylate) (PEB). However, the use of metal-free organocatalysis has several advantages, such as the reduction of toxic and expensive metals. In this work, a novel cellulose nanofibril (CNF)/PEB nanocomposite fabrication process by organocatalysis and reactive extrusion (REx) is disclosed. Here, ROP was carried out via solvent-free REx in the presence of CNFs using organic 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Neat or lactate-esterified CNFs (LACNF) were used as initiators to investigate the effect of surface topochemistry on the in situ polymerization and the properties of the nanocomposites. A molar mass of 9 kDa was achieved in the presence of both unmodified and LACNFs with high monomer conversion (>98%) after 30 min reaction in a microcompounder at 130 °C. Tensile analysis showed that both nanofibril types reinforce the matrix and increase its elasticity due to the efficient dispersion obtained through the grafting from polymerization achieved during the REx. Mechanical recycling of the neat polymer and the nanocomposites was proven as a circular solution for the materials' end-of-life and showed that lactate moieties induced some degradation.
Disciplines :
Chemistry
Author, co-author :
Avella, Angelica ; Department of Industrial and Materials Science, Chalmers University of Technology, Rännvägen 2A, Göteborg 41258, Sweden
Rafi, Abdolrahim; Department of Natural Sciences, Mid Sweden University, Holmgatan 10, Sundsvall 85170, Sweden
Deiana, Luca; Department of Natural Sciences, Mid Sweden University, Holmgatan 10, Sundsvall 85170, Sweden
MINCHEVA, Rosica ; Université de Mons - UMONS > Faculté des Sciences > Service des Matériaux Polymères et Composites
Córdova, Armando ; Department of Natural Sciences, Mid Sweden University, Holmgatan 10, Sundsvall 85170, Sweden
Lo Re, Giada ; Department of Industrial and Materials Science, Chalmers University of Technology, Rännvägen 2A, Göteborg 41258, Sweden
Language :
English
Title :
Organo-Mediated Ring-Opening Polymerization of Ethylene Brassylate from Cellulose Nanofibrils in Reactive Extrusion.
Vetenskapsr??det European Commission European Commission Chalmers Tekniska H??gskola Knut och Alice Wallenbergs Stiftelse Mittuniversitetet Gouvernement Wallon Wallenberg Wood Science Center
Funding text :
GLR acknowledges Knut and Alice Wallenberg Biocomposites [grant number V-2019-0041, Dnr. KAW 2018.0551], Wallenberg Wood Science Center program 3.0 and Chalmers Genie for financial support. Financial support by the Swedish National Research Council (VR), Mid Sweden University, and the European Union is also acknowledged. R.M. acknowledges the financial support from the FEDER and Wallonia in the frame of the LCFM-BIOMAT_1 project.
Rosenboom, J. G.; Langer, R.; Traverso, G. Bioplastics for a Circular Economy. Nat. Rev. Mater. 2022, 7 ( 2), 117- 137, 10.1038/s41578-021-00407-8
Müller, S.; Uyama, H.; Kobayashi, S. Lipase-Catalyzed Ring-Opening Polymerization of Cyclic Diesters. Chem. Lett. 1999, 28 ( 12), 1317- 1318, 10.1246/cl.1999.1317
Butron, A.; Llorente, O.; Fernandez, J.; Meaurio, E.; Sarasua, J. R. Morphology and Mechanical Properties of Poly(Ethylene Brassylate)/Cellulose Nanocrystal Composites. Carbohydr. Polym. 2019, 221 ( June), 137- 145, 10.1016/j.carbpol.2019.05.091
Fernández, J.; Amestoy, H.; Sardon, H.; Aguirre, M.; Varga, A. L.; Sarasua, J. R. Effect of Molecular Weight on the Physical Properties of Poly(Ethylene Brassylate) Homopolymers. J. Mech. Behav. Biomed. Mater. 2016, 64, 209- 219, 10.1016/j.jmbbm.2016.07.031
He, M.; Cheng, Y.; Liang, Y.; Xia, M.; Leng, X.; Wang, Y.; Wei, Z.; Zhang, W.; Li, Y. Amino Acid Complexes with Tin as a New Class of Catalysts with High Reactivity and Low Toxicity towards Biocompatible Aliphatic Polyesters. Polym. J. 2020, 52 ( 6), 567- 574, 10.1038/s41428-020-0314-0
Jin, C.; Wei, Z.; Yu, Y.; Sui, M.; Leng, X.; Li, Y. Copolymerization of Ethylene Brassylate with δ-Valerolactone towards Isodimorphic Random Copolyesters with Continuously Tunable Mechanical Properties. Eur. Polym. J. 2018, 102, 90- 100, 10.1016/j.eurpolymj.2018.03.018
Li, J.; Wang, S.; Lu, H.; Tu, Y.; Wan, X.; Li, X.; Tu, Y.; Li, C. Y. Helical Crystals in Aliphatic Copolyesters: From Chiral Amplification to Mechanical Property Enhancement. ACS Macro Lett. 2023, 12 ( 3), 369- 375, 10.1021/acsmacrolett.2c00753
Wang, X.; Wang, X.; Zhen, N.; Gu, J.; Zhang, H.; Dong, B.; Wang, F.; Liu, H. Sodium Complexes Bearing Cavity-like Conformations: A Highly Active and Well-Controlled Catalytic System for Macrolactone Homo- and Copolymerization. Polym. Chem. 2021, 12 ( 13), 1957- 1966, 10.1039/D0PY01580F
Wei, Z.; Jin, C.; Xu, Q.; Leng, X.; Wang, Y.; Li, Y. Synthesis, Microstructure and Mechanical Properties of Partially Biobased Biodegradable Poly (Ethylene Brassylate- Co - ϵ -Caprolactone) Copolyesters. J. Mech. Behav. Biomed. Mater. 2019, 91 ( December 2018), 255- 265, 10.1016/j.jmbbm.2018.12.019
Pascual, A.; Sardon, H.; Veloso, A.; Ruipérez, F.; Mecerreyes, D. Organocatalyzed Synthesis of Aliphatic Polyesters from Ethylene Brassylate: A Cheap and Renewable Macrolactone. ACS Macro Lett. 2014, 3 ( 9), 849- 853, 10.1021/mz500401u
Pascual, A.; Sardón, H.; Ruipérez, F.; Gracia, R.; Sudam, P.; Veloso, A.; Mecerreyes, D. Experimental and Computational Studies of Ring-Opening Polymerization of Ethylene Brassylate Macrolactone and Copolymerization with ϵ-Caprolactone and TBD-Guanidine Organic Catalyst. J. Polym. Sci., Part A: Polym. Chem. 2015, 53 ( 4), 552- 561, 10.1002/pola.27473
Kim, S.; Chung, H. Synthesis and Characterization of Lignin-Graft-Poly(Ethylene Brassylate): A Biomass-Based Polyester with High Mechanical Properties. ACS Sustain. Chem. Eng. 2021, 9 ( 44), 14766- 14776, 10.1021/acssuschemeng.1c04334
Fritz-Langhals, E. Unique Superbase TBD (1,5,7-Triazabicyclo[4.4.0]Dec-5-Ene): From Catalytic Activity and One-Pot Synthesis to Broader Application in Industrial Chemistry. Org. Process Res. Dev. 2022, 26 ( 11), 3015- 3023, 10.1021/acs.oprd.2c00248
Ottou, W. N.; Sardon, H.; Mecerreyes, D.; Vignolle, J.; Taton, D. Update and Challenges in Organo-Mediated Polymerization Reactions. Prog. Polym. Sci. 2016, 56, 64- 115, 10.1016/j.progpolymsci.2015.12.001
Spinella, S.; Ganesh, M.; Lo Re, G.; Zhang, S.; Raquez, J. M.; Dubois, P.; Gross, R. A. Enzymatic Reactive Extrusion: Moving towards Continuous Enzyme-Catalysed Polyester Polymerisation and Processing. Green Chem. 2015, 17 ( 8), 4146- 4150, 10.1039/C5GC00992H
Eichhorn, S. J.; Dufresne, A.; Aranguren, M.; Marcovich, N. E.; Capadona, J. R.; Rowan, S. J.; Weder, C.; Thielemans, W.; Roman, M.; Renneckar, S.; Gindl, W.; Veigel, S.; Keckes, J.; Yano, H.; Abe, K.; Nogi, M.; Nakagaito, A. N.; Mangalam, A.; Simonsen, J.; Benight, A. S.; Bismarck, A.; Berglund, L. A.; Peijs, T. Review: Current International Research into Cellulose Nanofibres and Nanocomposites. J. Mater. Sci. 2010, 45 ( 1), 1- 33, 10.1007/s10853-009-3874-0
Carlmark, A.; Larsson, E.; Malmström, E. Grafting of Cellulose by Ring-Opening Polymerisation - A Review. Eur. Polym. J. 2012, 48 ( 10), 1646- 1659, 10.1016/j.eurpolymj.2012.06.013
Hafrén, J.; Córdova, A. Direct Organocatalytic Polymerization from Cellulose Fibers. Macromol. Rapid Commun. 2005, 26 ( 2), 82- 86, 10.1002/marc.200400470
Córdova, A.; Hafrén, J. Direct Organic Acid-Catalyzed Polyester Derivatization of Lignocellulosic Material. Nord. Pulp Pap. Res. J. 2005, 20 ( 4), 477- 480, 10.3183/npprj-2005-20-04-p477-480
Casas, J.; Persson, P. V.; Iversen, T.; Córdova, A. Direct Organocatalytic Ring-Opening Polymerizations of Lactones. Adv. Synth. Catal. 2004, 346 ( 9-10), 1087- 1089, 10.1002/adsc.200404082
Rafi, A. A.; Alimohammadzadeh, R.; Avella, A.; Mõistlik, T.; Jűrisoo, M.; Kaaver, A.; Tai, C. W.; Lo Re, G.; Cordova, A. A Facile Route for Concurrent Fabrication and Surface Selective Functionalization of Cellulose Nanofibers by Lactic Acid Mediated Catalysis. Sci. Rep. 2023, 13 ( 1), 14730, 10.1038/s41598-023-41989-3
Lipik, V. T.; Widjaja, L. K.; Liow, S. S.; Abadie, M. J. M.; Venkatraman, S. S. Effects of Transesterification and Degradation on Properties and Structure of Polycaprolactone-Polylactide Copolymers. Polym. Degrad. Stab. 2010, 95 ( 12), 2596- 2602, 10.1016/j.polymdegradstab.2010.07.027
Collins, S.; Kenwright, A. M.; Pawson, C.; Peace, S. K.; Richards, R. W.; MacDonald, W. A.; Mills, P. Transesterification in Mixtures of Poly(Ethylene Terephthalate) and Poly(Ethylene Naphthalene-2,6-Dicarboxylate): An NMR Study of Kinetics and End Group Effects. Macromolecules 2000, 33 ( 8), 2974- 2980, 10.1021/ma9916382
Zhu, Z.; Xiong, C.; Zhang, L.; Deng, X. Synthesis and Characterization of Poly(?-Caprolactone)-Poly(Ethylene Glycol) Block Copolymer. J. Polym. Sci., Part A: Polym. Chem. 1997, 35 ( 4), 709- 714, 10.1002/(SICI)1099-0518(199703)35:4<709::AID-POLA14>3.0.CO;2-R
Carrasco, F.; Pagès, P.; Gámez-Pérez, J.; Santana, O. O.; Maspoch, M. L. Processing of Poly(Lactic Acid): Characterization of Chemical Structure, Thermal Stability and Mechanical Properties. Polym. Degrad. Stab. 2010, 95 ( 2), 116- 125, 10.1016/j.polymdegradstab.2009.11.045
Liu, P.; Wu, J.; Yang, G.; Shao, H. Comparison of Static Mixing Reaction and Reactive Extrusion Technique for Ring-Opening Polymerization of L-Lactide. Mater. Lett. 2017, 186 ( September 2016), 372- 374, 10.1016/j.matlet.2016.10.024
Magnani, C.; Idström, A.; Nordstierna, L.; Müller, A. J.; Dubois, P.; Raquez, J. M.; Lo Re, G. Interphase Design of Cellulose Nanocrystals/Poly(Hydroxybutyrate- Ran-Valerate) Bionanocomposites for Mechanical and Thermal Properties Tuning. Biomacromolecules 2020, 21 ( 5), 1892- 1901, 10.1021/acs.biomac.9b01760
Spinella, S.; Lo Re, G.; Liu, B.; Dorgan, J.; Habibi, Y.; Leclère, P.; Raquez, J. M.; Dubois, P.; Gross, R. A. Polylactide/Cellulose Nanocrystal Nanocomposites: Efficient Routes for Nanofiber Modification and Effects of Nanofiber Chemistry on PLA Reinforcement. Polymer 2015, 65, 9- 17, 10.1016/j.polymer.2015.02.048
Marxsen, S. F.; Song, D.; Zhang, X.; Flores, I.; Fernández, J.; Sarasua, J. R.; Müller, A. J.; Alamo, R. G. Crystallization Rate Minima of Poly(Ethylene Brassylate) at Temperatures Transitioning between Quantized Crystal Thicknesses. Macromolecules 2022, 55, 3958- 3973, 10.1021/acs.macromol.2c00308
Román-Ramírez, L. A.; McKeown, P.; Shah, C.; Abraham, J.; Jones, M. D.; Wood, J. Chemical Degradation of End-of-Life Poly(Lactic Acid) into Methyl Lactate by a Zn(II) Complex. Ind. Eng. Chem. Res. 2020, 59 ( 24), 11149- 11156, 10.1021/acs.iecr.0c01122
Avella, A.; Mincheva, R.; Raquez, J.-M.; Lo Re, G. Substantial Effect of Water on Radical Melt Crosslinking and Rheological Properties of Poly(ϵ-Caprolactone). Polymers 2021, 13 ( 4), 491- 505, 10.3390/polym13040491
Hill, A.; Ronan, W. Relationship between Failure Strain, Molecular Weight, and Chain Extensibility in Biodegradable Polymers. J. Mech. Behav. Biomed. Mater. 2023, 139 ( October 2022), 105663, 10.1016/j.jmbbm.2023.105663
