Synthesis and Characterization of Terpenoid-derived Poly(6,10-dimethyl-1,3,9-undecatriene): A Biobased and Sustainable Polymer from Renewable Citronellal

Xin Li; Feng Wang; Qi Yang; Xue-Quan Zhang; Heng Liu

doi:10.1007/s10118-025-3408-5

Your Location：

Home >

Browse articles >

Synthesis and Characterization of Terpenoid-derived Poly(6,10-dimethyl-1,3,9-undecatriene): A Biobased and Sustainable Polymer from Renewable Citronellal

RESEARCH ARTICLE | Updated：2025-09-26

- Synthesis and Characterization of Terpenoid-derived Poly(6,10-dimethyl-1,3,9-undecatriene): A Biobased and Sustainable Polymer from Renewable Citronellal
- Chinese Journal of Polymer Science Vol. 43, Issue 10, Pages: 1825-1836(2025)
- Affiliations：
  
  Shandong Provincial College Laboratory of Rubber Material and Engineering/ Key Laboratory of Rubber-Plastics, Ministry of Education, Qingdao University of Science & Technology, Qingdao 266042, China
- Author bio：
  
  qyang@qust.edu.cn (Q. Y.)
  hengliu@qust.edu.cn (H. L.)
- Funds：
- DOI：10.1007/s10118-025-3408-5
  CLC：
- Received：20 May 2025，
  
  Revised：2025-06-19，
  
  Accepted：30 June 2025，
  
  Online First：10 September 2025，
  
  Published：05 October 2025
- Accepted：
Scan QR Code
Li, X.; Wang, F.; Yang, Q.; Zhang, X. Q.; Liu, H. Synthesis and characterization of terpenoid-derived poly(6,10-dimethyl-1,3,9-undecatriene): a biobased and sustainable polymer from renewable citronellal. Chinese J. Polym. Sci. 2025, 43, 1825–1836

Xin Li, Feng Wang, Qi Yang, et al. Synthesis and Characterization of Terpenoid-derived Poly(6,10-dimethyl-1,3,9-undecatriene): A Biobased and Sustainable Polymer from Renewable Citronellal[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1825-1836.
Li, X.; Wang, F.; Yang, Q.; Zhang, X. Q.; Liu, H. Synthesis and characterization of terpenoid-derived poly(6,10-dimethyl-1,3,9-undecatriene): a biobased and sustainable polymer from renewable citronellal. Chinese J. Polym. Sci. 2025, 43, 1825–1836 DOI： 10.1007/s10118-025-3408-5.

Xin Li, Feng Wang, Qi Yang, et al. Synthesis and Characterization of Terpenoid-derived Poly(6,10-dimethyl-1,3,9-undecatriene): A Biobased and Sustainable Polymer from Renewable Citronellal[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1825-1836. DOI： 10.1007/s10118-025-3408-5.

摘要

This study presents an innovative approach to synthesize bio-based polydiene polymers from citronellall by converting it into the diene monomer 6

10-dimethyl-1

9-undecatriene (DMUT) via Wittig reaction

followed by neodymium-catalyzed polymerization.

Abstract

As a naturally occurring terpenoid that is abundant in essential oils

citronellal remains largely unexplored in polymer science. Herein

we present a novel strategy for converting bio-based citronellal into the diene monomer 6

10-dimethyl-1

9-undecatriene (DMUT)

which undergoes neodymium-catalyzed coordination polymerization to yield poly(6

10-dimethyl-1

9-undecatriene) (PDMUT)

a bio-derived polydiene polymer. This provides a facile and sustainable route for transforming renewable citronellal into functional polymers. The effects of polymerization conditions on the catalytic performance and polymer characteristics

including molecular weight

polydispersity

and microstructure

were systematically investigated. In addition

DMUT was successfully copolymerized with isoprene (IP) and 1

3-butadiene (BD)

yielding copolymers with tunable compositions and microstructures. These results demonstrate the versatility of DMUT as a renewable building block for both homopolymers and copolymers

paving the way toward bio-based elastomeric materials with customizable properties.

关键词

Keywords

references

Wang, Z.; Ganewatta, M. S.; Tang, C. Sustainable polymers from biomass: bidging chemistry with materials and processing. Prog. Polym. Sci. 2020 , 101 , 101197..

Liu, J.; Wang, S.; Peng, Y.; Zhu, J.; Zhao, W.; Liu, X. Advances in sustainable thermosetting resins: From renewable feedstock to high performance and recyclability. Prog. Polym. Sci. 2021 , 113 , 101353..

Rosenboom, J. G.; Langer, R.; Traverso, G. Bioplastics for a circular economy. Nat. Rev. Mater. 2022 , 7 , 117−137..

Ganewatta, M. S.; Wang, Z.; Ta ng, C. Chemical syntheses of bioinspired and biomimetic polymers toward biobased materials. Nat. Rev. Chem. 2021 , 5 , 753−772..

Lamparelli, D. H.; Winnacker, M.; Capacchione, C. Stereoregular polymerization of acyclic terpenes. ChemPlusChem 2022 , 87 , e202100366..

Bakkali, F.; Averbeck, S.; Averbeck, D.; Idaomar, M. Biological effects of essential oils—a review. Food Chem. Toxicol. 2008 , 46 , 446−475..

Wahlen, C.; Frey, H. Anionic polymerization of terpene monomers: new options for bio-based thermoplastic elastomers. Macromolecules 2021 , 54 , 7323−7336..

[Zhao, J.; Schlaad, H., Synthesis of terpene-based polymers. In bio-synthetic polymer conjugates , Schlaad, H., Ed. Springer Berlin Heidelberg: Berlin, Heidelberg, 2013 , pp. 151–190..

Winnacker, M. Terpene-based polyamides: a sustainable polymer class with huge potential. Curr. Opin. Green Sust. 2023 , 41 , 100819..

[Kamigaito, M.; Satoh, K., Sustainable vinyl polymers via controlled polymerization of terpenes. In Sustainable Polymers from Biomass , 2017 , pp. 55−90..

Zhu, Y.; Romain, C.; Williams, C. K. Sustainable polymers from renewable resources. Nature 2016 , 540 , 354−362..

[Georges, S.; Bria, M.; Zinck, P.; Visseaux, M. Polymyrcene microstructure revisited from precise high-field nuclear magnetic resonance analysis. Polymer 2024 , 55 , 3869−3878..

Loughmari, S.; Hafid, A.; Bouazza, A.; El Bouadili, A.; Zinck, P.; Visseaux, M. Highly stereoselective coordination polymerization of β-myrcene from a lanthanide-based catalyst: access to bio-sourced elastomers. J. Polym. Sci. Polym. Chem. 2012 , 50 , 2898−2905..

Liu, B.; Li, L.; Sun, G.; Liu, D.; Li, S.; Cui, D. Isoselective 3,4-(co)polymerization of bio-renewable myrcene using NSN-ligated rare-earth metal precursor: an approach to a new elastomer. Chem. Commun. 2015 , 51 , 1039−1041..

Liu, B.; Liu, D.; Li, S.; Sun, G.; Cui, D. High trans-1,4 (co)polymerization of β -myrcene and isoprene with an iminophosphonamide lanthanum catalyst. Chinese J. Polym. Sci. 2016 , 34 , 104−110..

Métafiot, A.; Kanawati, Y.; Gérard, J.-F.; Defoort, B.; Marić, M. Synthesis of β -myrcene-based polymers and styrene block and statistical copolymers by SG1 nitroxide-mediated controlled radical plymerization. Macromolecules 2017 , 50 , 3101−3120..

Jia, X.; Li, W.; Zhao, J.; Yi, F.; Luo, Y.; Gong, D. Dual catalysis of the selective polymerization of biosourced myrcene and methyl methacrylate promoted by salicylaldiminato cobalt(II) complexes with a pendant donor. Organometallics 2018 , 38 , 278−288..

Ren, X.; Guo, F.; Fu, H.; Song, Y.; Li, Y.; Hou, Z. Scandium-catalyzed copolymerization of myrcene with ethylene and propylene: convenient syntheses of versatile functionalized polyolefins. Polym. Chem. 2018 , 9 , 1223−1233..

Li, W.; Zhao, J.; Zhang, X.; Gong, D. Capability of PN3-type cobalt complexes toward selective (co-)polymerization of myrcene, butadiene, and isoprene: access to biosourced polymers. Ind. Eng. Chem. Res. 2019 , 58 , 2792−2800..

Yu, X.; Li, M.; Hong, J.; Zhou, X.; Zhang, L. Living 3,4-(co)polymerization of isoprene/myrcene and one-pot synthesis of a polyisoprene blend catalyzed by binuclear rare-earth metal amidinate complexes. Chem. Eur. J. 2019 , 25 , 2569−2576..

[Xu, Y.; Zhao, J.; Gan, Q.; Ying, W.; Hu, Z.; Tang, F.; Luo, W.; Luo, Y.; Jian, Z.; Gong, D. Synthesis and properties investigation of hydroxyl functionalized polyisoprene prepared by cobalt catalyzed co-polymerization of isoprene and hydroxylmyrcene. Polym. Chem . 2020 , 11 , 2034−2043..

Kitphaitun, S.; Chaimongkolkunasin, S.; Manit, J.; Makino, R.; Kadota, J.; Hirano, H.; Nomura, K. Ethylene/myrcene copolymers as new bio-based elastomers prepared by coordination polymerization using titanium catalysts. Macromolecules 2021 , 54 , 10049−10058..

Wang, Q. Y.; Sang, L. P.; Zhang, Z.; Jiang, Y.; Tian, H.; Zhao, X.; Guo, X.; Li, S.-H. Regio- and stereoselective polymerization of bio-based ocimene by rare-earth metal catalysts. Chinese J. Polym. Sci. 2024 , 42 , 223−229..

Wadgaonkar, S. P.; Wagner, M.; Baptista, L. A.; Cortes-Huerto, R.; Frey, H.; Müller, A. H. E. Anionic polymerization of the terpene-based diene β-ocimene: complex mechanism due to stereoisomer reactivities. Macromolecules 2023 , 56 , 664−677..

Radchenko, A. V.; Bouchekif, H.; Peruch, F. Triflate esters as in-situ generated initiating system for carbocationic polymerization of vinyl ethers, isoprene, myrcene and ocimene. Eur. Polym. J. 2017 , 89 , 34−41..

Peng, D.; Du, G.; Zhang, P.; Yao, B.; Li, X.; Zhang, S. Regio- and stereochemical control in ocimene polymerization by half-sandwich rare-earth metal dialkyl complexes. Macromol. Rapid Commun. 2016 , 37 , 987−992..

Naddeo, M.; Buonerba, A.; Luciano, E.; Grassi, A.; Proto, A.; Capacchione, C. Stereoselective polymerization of biosourced terpenes β -myrcene and β -ocimene and their copolymerization with styrene promoted by titanium catalysts. Polymer 2017 , 131 , 151−159..

Lamparelli, D. H.; Paradiso, V.; Monica, F. D.; Proto, A.; Guerra, S.; Giannini, L.; Capacchione, C. Toward more sustainable elastomers: stereoselective copolymerization of linear terpenes with butadiene. Macromolecules 2020 , 53 , 1665−1678..

Sahu, P.; Bhowmick, A. K. Redox emulsion polymerization of terpenes: mapping the effect of the system, structure, and reactivity. Ind. Eng. Chem. Res. 2019 , 58 , 20946−20960..

Lamparelli, D. H.; Paradiso, V.; Capacchione, C. New elastomeric materials from biomass: stereoselective polymerization of linear terpenes and their copolymerization with butadiene by using a cobalt complex with phosphane ligands. Rub. Chem. Technol. 2020 , 93 , 605−614..

Luk, S. B.; Maríc, M. Polymerization of biobased farnesene in miniemulsions by nitroxide-mediated polymerization. ACS Omega 2021 , 6 , 4939−4949..

You, F.; Kang, X.; Nishiura, M.; Zhai, J.; Xu, S.; Wang, J.; Shi, X.; Hou, Z. Living 3,4-isoselective (co)polymerization of biobased β-farnesene catalyzed by phosphine-functionalized fluorenyl rare-earth metal catalysts. Macromolecules 2022 , 55 , 5049−5057..

Luk, S. B.; Maric, M. Farnesene and norbornenyl methacrylate block copolymers: application of thiol-ene clicking to improve thermal and mechanical properties. Polymer 2021 , 230 , 124106..

Jiang, Y.; Zhang, Z.; Li, S.; Cui, D. Coordination polymerization of renewable (E)-4,8-dimethyl-1,3,7-nonatriene by rare-earth metal catalysts. Chin. J. Chem. 2022 , 40 , 1939−1944..

Sahu, P.; Sarkar, P.; Bhowmick, A. K. Synthesis and characterization of a terpene-based sustainable polymer: poly-alloocimene. ACS Sustain. Chem. Eng. 2017 , 5 , 7659−7669..

Jones, J. F. Cyclopolymerization. III. poly-alloocimene. J. Polym. Sci. 1958 , 33 , 513−515..

Puskas, J. E.; Gergely, A. L.; Kaszas, G. Controlled/living carbocationic copolymerization of isobutylene with alloocimene. J. Polym. Sci. Polym. Chem. 2013 , 51 , 29−33..

Gergely, A. L.; Puskas, J. E. Synthesis and characterization of thermoplastic elastomers with polyisobutyl ene and polyalloocimene blocks. J. Polym. Sci. Polym. Chem. 2015 , 53 , 1567−1574..

[Venancio, A. N.; Silva, M. J.; Parreira, L. A.; Júlio, A. A.; Souza, G. R.; Conceição Santos, M. F.; Menini, L. Citronellall: a natural aldehyde with important properties. Nat. Prod. Res. 2025 , 39 , 1199−1212..

[Rokonuzzman, M.; Bhuia, M. S.; Al-Qaaneh, A. M.; El-Nashar, H. A. S.; Islam, T.; Chowdhury, R.; Hasan Shanto, H.; Al Hasan, M. S.; El-Shazly, M.; Torequl Islam, M. Biomedical perspectives of citronellall: biological activities, toxicological profile and molecular mechanisms. Chem. Biodivers. 2025 , 22 , 202401973..

Mäki-Arvela, P.; Simakova, I.; Vajglová, Z.; Murzin, D. Y. One-pot synthesis of menthol from citral and citronellall over heterogeneous catalysts. Catal. Surv. Asia 2023 , 27 , 2−19..

Ricci, G.; Zetta, L.; Porri, L.; Meille, S. V. Synthesis and characterization of isotactic cis-1,4-poly(3-methyl-1,3-pentadiene). Macromol. Chem. Phys. 1995 , 196 , 2785−2793..

Hu, Y.; Dong, W.; Masuda, T. Novel methylaluminoxane-activated neodymium isopropoxide catalysts for 1,3-butadiene polymerization and 1,3-butadiene/isoprene copolymerization. Macromol. Chem. Phys. 2013 , 214 , 2172−2180..

Wang, F.; Liu, H.; Hu, Y.; Zhang, X. Lanthanide complexes mediated coordinative chain transfer polymerization of conjugated dienes. Sci. China Technol. Sci. 2018 , 61 , 1286−1294..

Leone, G.; Caterina Boccia, A.; Ricci, G.; Giarrusso, A.; Porri, L. Polymerization of (E)-1,3-pentadiene and (E)-2-methyl-1,3-pentadiene with neodymium catalysts: examination of the factors that affect the stereoselectivity. J. Polym. Sci. Polym. Chem. 2013 , 51 , 3227−3232..

Ricci, G.; Boccia, A. C.; Palucci, B.; Sommazzi, A.; Masi, F.; Scoti, M.; De Stefano, F.; De Rosa, C. Synthesis of stereoregular polymyrcenes using neodymium-, iron- and copper-based catalysts. Polym. Chem. 2024 , 15 , 1367−1376..

Gan, Q.; Xu, Y.; Huang, W.; Luo, W.; Hu, Z.; Tang, F.; Jia, X.; Gong, D. Utilization of bio-sourced myrcene for efficient preparation of highly cis-1,4 regular elastomer via a neodymium catalyzed copolyme rization strategy. Polym. Int. 2020 , 69 , 763−770..

Wang, F.; Zhang, C.; Hu, Y.; Jia, X.; Bai, C.; Zhang, X. Reversible coordinative chain transfer polymerization of isoprene and copolymerization with ε -caprolactone by neodymium-based catalyst. Polymer 2012 , 53 , 6027−6032..

Cheng, L.; Li, M. M.; Xiao, L. J.; Xie, J. H.; Zhou, Q. L. Nickel(0)-catalyzed hydroalkylation of 1,3-dienes with simple ketones. J. Am. Chem. Soc. 2018 , 140 , 11627−11630..

Timsina, Y. N.; Biswas, S.; RajanBabu, T. V. Chemoselective reactions of (E)-1,3-dienes: cobalt-mediated isomerization to ( Z )-1,3-dienes and reactions with ethylene. J. Am. Chem. Soc. 2014 , 136 , 6215−6218..

[Friebe, L.; Windisch, H.; Nuyken, O.; Obrecht, W. Polymerization of 1,3-butadiene initiated by neodymium versatate/triisobutylaluminum/ethylaluminum sesquichloride: impact of the alkylaluminum cocatalyst component. J. Macromol. Sci. Pur . 2004, A41 , 245−256..

Wang, F.; Liu, H.; Zheng, W.; Guo, J.; Zhang, C.; Zhao, L.; Zhang, H.; Hu, Y.; Bai, C.; Zhang, X. Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems. Polymer 2013 , 54 , 6716−6724..

[Friebe, L.; Nuyken, O.; Obrecht, W. in Neodymium-based Ziegler/Natta catalysts and their application in diene polymerization . Springer-Verlag Berlin Heidelbery, 2006 , pp. 9−12..

Liu, X.; Zheng, H.; Wang, X.; Jiang, Z.; Gu, J.; Liu, H.; Zhang, C.; Yang, Q.; Zhang, X. Novel butadiene/isoprene copolymer with predominant 1,2/3,4-units: a tough thermoplastic elastomer material with superior dynamic mechanical properties. Eur. Polym. J. 2023 , 196 , 112333..

Views

541

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Synthesis and Performance Evaluation of Degradable Sorbitol-derived Epoxy Resins

Unleashing the Power of Bio-based Thermotropic Liquid Crystal Modifiers: Toughening and Reinforcing Petroleum-based Epoxy Resin without Compromising Other Properties

Chemical Recycling of Poly(ethylene furanoate) into Value-added Poly(ethylene-co-isosorbide furanoate)

Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

Circularly Polarized Luminescence Based on Helical Polymers: Structure-Property Relationships and Regulation Mechanisms

Related Author

Huai-Qing Tian

Xin-Xin Zhou

Xiang-Qing Li

He-Chen Liu

Zhi-Huan Weng

Xi-Gao Jian

Yan Kou

Bei-Tao Liu

Related Institution

Hebei Key Laboratory of Green and Efficient New Electrical Materials and Equipment, North China Electric Power University

State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Liaoning Technology Innovation Center of High Performance Resin Materials, Department of Polymer Science & Engineering, Dalian University of Technology

Thermochemistry Laboratory, Liaoning Province Key Laboratory of Thermochemistry for Energy and Materials, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University

Jiangsu Key Laboratory for Micro and Nano Heat Fluid Flow Technology and Energy Application, School of Physical Science and Technology, Suzhou University of Science and Technology

⁰