Ring-opening polymerization of ethylene brassylate in reactive extrusion and its end-of-life options

Compost; Enzymatic depolymerization; Ethylene brassylate; Reactive extrusion; End of lives; End-of-life options; Lipase B from Candida antarctica; Poly(ethylenes); Reactive extrusions; Renewables; Ring-opening polymerization; Synthesised; Condensed Matter Physics; Mechanics of Materials; Polymers and Plastics; Materials Chemistry

Abstract :

[en] Polyesters synthesised from renewable monomers via intensified and industrially relevant processes provide nowadays a science-to-technology breakthrough, especially if they offer a suitable end-of-life scenario for a circular economy. In this work bio-based macrolactone ethylene brassylate was polymerized by reactive extrusion and the properties of the polyester and its end-of-life options were studied. The ring-opening polymerization was tested with several catalytic systems, among which the organic base 1,5,7-triazabicyclo[4.4.0]dec-5-en (TBD) and the immobilized enzymes Lipase B from Candida antarctica and Lipase from Pseudomonas cepacia successfully synthesised poly(ethylene brassylate) (PEB). TBD served as both catalyst and initiator, yielding PEB with a molar mass of 8000 g/mol, melting temperature around 70 °C and main degradation temperature of 440 °C. Tensile tests showed that PEB had a brittle behaviour with Young's modulus of 290 MPa and elongation at break of 4 %. PEB lost 93 % of its initial weight after 90 days in compost, degrading through surface erosion. Lipase B from Candida antarctica was demonstrated successful for the enzymatic depolymerization. Therefore, enzymatic depolymerization and disintegration in compost were suggested as feasible pathways for PEB circular design.

Disciplines :

Chemistry

Author, co-author :

Lo Re, Giada ; Department of Industrial and Materials Science, Chalmers University of Technology, Gothenburg, Sweden ; Wallenberg Wood Science Center, Chalmers University of Technology, Gothenburg, Sweden

Avella, Angelica ; Department of Industrial and Materials Science, Chalmers University of Technology, Gothenburg, Sweden ; Wallenberg Wood Science Center, Chalmers University of Technology, Gothenburg, Sweden

Pappalardo, Daniela; Dipartimento di Scienze e Tecnologie, Università del Sannio, Via de Sanctis snc, Italy

Mincheva, Rosica ; Université de Mons - UMONS > Faculté des Sciences > Service des Matériaux Polymères et Composites

Language :

English

Title :

Ring-opening polymerization of ethylene brassylate in reactive extrusion and its end-of-life options

Publication date :

April 2025

Journal title :

Polymer Degradation and Stability

ISSN :

0141-3910

eISSN :

1873-2321

Publisher :

Elsevier Ltd

Volume :

234

Pages :

111203

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://api.elsevier.com/content/article/PII:S0141391025000345?httpAccept=text/xml

Research unit :

S816 - Matériaux Polymères et Composites

Research institute :

Research Institute for Materials Science and Engineering

Funders :

Knut and Alice Wallenberg Foundation
Waalse Gewest
European Regional Development Fund
Wallenberg Wood Science Center

Funding text :

This work was supported by the Knut and Alice Wallenberg Foundation (KAW) through the Wallenberg Wood Science Center (WWSC 3.0: KAW 2021.0313, project number II-15), the European Regional Development Fund and the Walloon Region grants LCFM-BIOMAT and Bioprofiling platform.

Available on ORBi UMONS :

since 11 December 2025

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Bibliography

Mohanty, A.K., Wu, F., Mincheva, R., Hakkarainen, M., Raquez, J.-M., Mielewski, D.F., Narayan, R., Netravali, A.N., Misra, M., Sustainable polymers. Nat. Rev. Methods Prim., 2, 2022, 46, 10.1038/s43586-022-00124-8.
European Parliament. Sustainable Waste Management: What the EU is Doing. 2024 https://www.europarl.europa.eu/topics/en/article/20180328STO00751/sustainable-waste-management-what-the-eu-is-doing (Accessed 4 April 2024).
European Bioplastics. Bioplastics Market Data. 2023 https://www.european-bioplastics.org/market/.
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. 64 (2016), 209–219, 10.1016/j.jmbbm.2016.07.031.
Müller, S., Uyama, H., Kobayashi, S., Lipase-catalyzed ring-opening polymerization of cyclic diesters. Chem. Lett. 28 (1999), 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. 221 (2019), 137–145, 10.1016/j.carbpol.2019.05.091.
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. 52 (2020), 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. 102 (2018), 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. 12 (2023), 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. 12 (2021), 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. 91 (2019), 255–265, 10.1016/j.jmbbm.2018.12.019.
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. 9 (2021), 14766–14776, 10.1021/ACSSUSCHEMENG.1C04334.
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. 3 (2014), 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 53 (2015), 552–561, 10.1002/POLA.27473.
Wilson, J.A., Ates, Z., Pflughaupt, R.L., Dove, A.P., Heise, A., Polymers from macrolactones: from pheromones to functional materials. Prog. Polym. Sci. 91 (2019), 29–50, 10.1016/j.progpolymsci.2019.02.005.
Wang, X., Zhao, W., Liu, H., Han, M., Zhang, C., Zhang, X., Wang, F., Potassium phenoxides bearing bulky yet flexible substituents as highly active catalysts for ring opening polymerization of biobased macrolactone of ethylene brassylate. Eur. Polym. J., 211, 2024, 112993, 10.1016/j.eurpolymj.2024.112993.
Liu, L., Zhang, C., Zhang, X., Liu, H., Wang, F., Efficient and well-controlled ring opening polymerization of biobased ethylene brassylate by α-diimine FeCl3 catalysts via a coordination–insertion mechanism. Dalt. Trans. 52 (2023), 17104–17108, 10.1039/D3DT02918B.
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. 17 (2015), 4146–4150, 10.1039/c5gc00992h.
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. 186 (2017), 372–374, 10.1016/j.matlet.2016.10.024.
Kim, I., White, J.L., Reactive copolymerization of various monomers based on lactams and lactones in a twin-screw extruder. J. Appl. Polym. Sci. 96 (2005), 1875–1887, 10.1002/APP.21494.
Avella, A., Rafi, A., Deiana, L., Mincheva, R., Córdova, A., Lo Re, G., Organo-mediated ring-opening polymerization of ethylene brassylate from cellulose nanofibrils in reactive extrusion. ACS Sustain. Chem. Eng. 12 (2024), 10727–10738, 10.1021/acssuschemeng.4c01309.
Deiana, L., Avella, A., Rafi, A.A., Mincheva, R., De Winter, J., Lo Re, G., Córdova, A., In situ enzymatic polymerization of ethylene brassylate mediated by artificial plant cell walls in reactive extrusion. ACS Appl. Polym. Mater. 6 (2024), 10414–10422, 10.1021/acsapm.4c01568.
Gorrasi, G., Pappalardo, D., Pellecchia, C., Polymerization of ε-caprolactone by sodium hydride: from the synthesis of the polymer samples to their thermal, mechanical and barrier properties. React. Funct. Polym. 72 (2012), 752–756, 10.1016/j.reactfunctpolym.2012.07.007.
Gorrasi, G., Meduri, A., Rizzarelli, P., Carroccio, S., Curcuruto, G., Pellecchia, C., Pappalardo, D., Preparation of poly(glycolide-co-lactide)s through a green process: analysis of structural, thermal, and barrier properties. React. Funct. Polym. 109 (2016), 70–78, 10.1016/j.reactfunctpolym.2016.10.002.
Fernández, J., Montero, M., Etxeberria, A., Sarasua, J.R., Ethylene brassylate: searching for new comonomers that enhance the ductility and biodegradability of polylactides. Polym. Degrad. Stab. 137 (2017), 23–34, 10.1016/J.POLYMDEGRADSTAB.2017.01.001.
Bian, X., Huang, S., Yan, X., Li, X., Wang, S., Tu, Y., Chemical recycling of poly(butylene terephthalate) into poly(ethylene brassylate- co -butylene terephthalate) with tunable thermal, mechanical and biodegradable properties. ACS Appl. Polym. Mater. 6 (2024), 7047–7056, 10.1021/acsapm.4c00832.
ISO, ISO 20200:2015(en). Plastics — Determination of the Degree of Disintegration of Plastic Materials Under Simulated Composting Conditions in a Laboratory-Scale Test. 2015.
Martínez-Cutillas, A., León, S., Oh, S., Martínez de Ilarduya, A., Enzymatic recycling of polymacrolactones. Polym. Chem. 13 (2022), 1586–1595, 10.1039/D1PY01721G.
Naumann, S., Scholten, P.B.V., Wilson, J.A., Dove, A.P., Dual catalysis for selective ring-opening polymerization of lactones: evolution toward simplicity. J. Am. Chem. Soc. 137 (2015), 14439–14445, 10.1021/JACS.5B09502.
Hua, G., Odelius, K., Exploiting ring-opening aminolysis–condensation as a polymerization pathway to structurally diverse biobased polyamides. Biomacromolecules 19 (2018), 1573–1581, 10.1021/acs.biomac.8b00322.
Kim, B.J., White, J.L., Bulk polymerization of ε-caprolactone in an internal mixer and in a twin screw extruder. Int. Polym. Process. 17 (2002), 33–43, 10.3139/217.1671.
Heise, A., Duxbury, C.J., Palmans, A.R.A., Enzyme-mediated ring-opening polymerization. Handbook of Ring-Opening Polymerization, 2009, Wiley, 379–397, 10.1002/9783527628407.ch15.
Shimokawa, K., Kato, M., Matsumura, S., Enzymatic synthesis and chemical recycling of polythiocaprolactone. Macromol. Chem. Phys. 212 (2011), 150–158, 10.1002/macp.201000488.
Kanbargi, N., Goswami, M., Collins, L., Kearney, L.T., Bowland, C.C., Kim, K., Rajan, K., Labbe, N., Naskar, A.K., Synthesis of high-performance lignin-based inverse thermoplastic vulcanizates with tailored morphology and properties. ACS Appl. Polym. Mater., 2021, 2911–2920, 10.1021/acsapm.0c01387.
Hakkarainen, M., Aliphatic polyesters: abiotic and biotic degradation and degradation products. Albertsson, A.-C., (eds.) Degradable Aliphatic Polyesters, 2002, Springer New York, 113–138, 10.1007/3-540-45734-8_4/COVER.
Partini, M., Pantani, R., FTIR analysis of hydrolysis in aliphatic polyesters. Polym. Degrad. Stab. 92 (2007), 1491–1497, 10.1016/j.polymdegradstab.2007.05.009.
Zhao, T., Sha, F., Xiao, J., Xu, Q., Xie, X., Zhang, J., Wei, X., Absorption, desorption and spectroscopic investigation of sulfur dioxide in the binary system ethylene glycol+dimethyl sulfoxide. Fluid Phase Equilib. 405 (2015), 7–16, 10.1016/j.fluid.2015.06.047.
Wang, G., Hui, Y., Wei, D., Wang, Y., Yu, Y., Shi, L., Zhang, M., Hu, J., Poly(butylene succinate-co-butylene brassylate) derived from brassylic acid: structures and properties. J. Polym. Environ. 32 (2024), 5689–5701, 10.1007/S10924-024-03330-5/FIGURES/7.