Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane <italic style="font-style: italic">via</italic> Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid

Xue-Qing Li; Shuai Lu; Jun-Jie Tan; Bo Lv; Hong-Ye Yan; Yan Tang; Yu Zhou; Yang Zhou; Hong-Xiang Chen

doi:10.1007/s10118-026-3686-6

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Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid

RESEARCH ARTICLE | Updated：2026-08-31

- Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid
- Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid
- Chinese Journal of Polymer Science 2026年44卷第9期页码：3042-3052
- Affiliations：
  
  a.School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China
  b.School of Textile Science and Engineering, State Key Laboratory of New Textile Materials and Advanced Processing Technology, Wuhan Textile University, Wuhan 430200, China
  c.Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, Hubei Normal University, Huangshi 435002, China
- Author bio：
  
  chenhongxiang@wust.edu.cn
- Funds：
  
  This work was financially supported by the Hubei Key Laboratory of Pollutant Analysis & Reuse Technology (No. PA230102). We would like to thank Feizhou Wang at the Analytical & Testing Center of Wuhan University of Science and Technology for his help with the XRD analysis.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3686-6.Data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3686-6
  中图分类号：
- 收稿：2026-01-31，
  
  录用：2026-03-26，
  
  网络首发：2026-06-11，
  
  纸质出版：2026-09-05
- Accepted：
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Li, X. Q.; Lu, S.; Tan, J. J.; Lv, B.; Yan, H. Y.; Tang, Y.; Zhou, Y.; Zhou, Y.; Chen, H. X. Two-way shape memory effect of polycaprolactone-based polyurethane via synergistic role of hydrogen bonding and crystallization tuned by malic acid. Chinese J. Polym. Sci. 2026, 44, 3042–3052

Xue-Qing Li, Shuai Lu, Jun-Jie Tan, et al. Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3042-3052. DOI: 10.1007/s10118-026-3686-6.
Li, X. Q.; Lu, S.; Tan, J. J.; Lv, B.; Yan, H. Y.; Tang, Y.; Zhou, Y.; Zhou, Y.; Chen, H. X. Two-way shape memory effect of polycaprolactone-based polyurethane via synergistic role of hydrogen bonding and crystallization tuned by malic acid. Chinese J. Polym. Sci. 2026, 44, 3042–3052 DOI： 10.1007/s10118-026-3686-6.

Xue-Qing Li, Shuai Lu, Jun-Jie Tan, et al. Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3042-3052. DOI: 10.1007/s10118-026-3686-6. DOI：

摘要

Malic acid

(MA) side chains were incorporated into the polycaprolactone (PCL)-based cross-linked polyurethane. The incorporation broadened the melting transition. The sample exhibited a steadier

act

and a higher

rec

during four heating-cooling cycles. The synergistic mechanism of dynamic MA-PCL hydrogen bonding and residual crystalline domains optimized the precision of deformation and cyclic stability.

Abstract

Semi-crystalline polymers can obtain a broad melting transition by copolymerization or blending and show a two-way shape memory effect (2W-SME) under stress-free conditions. However

intricate interactions between polymers are not easily controlled. It is still challenging for semi-crystalline polymers to obtain a two-way shape memory effect by broadening the melting transition. Here

we prepared polycaprolactone (PCL)-based cross-linked polyurethane by using malic acid as a side chain

thereby exploring the relationship between malic acid and the crystallinity of PCL or 2W-SME. The results showed that the incorporation of malic acid broadened the melting transition and improved the two-way shape memory behavior of the PCL-based cross-linked polyurethane. The influence of malic acid on the dynamic response mechanism of polyurethane was studied using

in situ

polarized optical microscopy (POM)

X-ray diffraction (XRD)

and Fourier transform infrared (FTIR) spectroscopy. The investigation revealed that the malic acid side chain plays a dual role by adjusting the crystallization behavior and strengthening the hydrogen-bonding network in the two-way shape memory process. This work provides a versatile strategy for the structural design of two-way shape memory polymers.

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Nordin, N. S.; Chen, X.; Fong, M. O.; Lok, T. J.; Xue, Y.; Li, S.; Feng, T.; Shen, Y.; Hu, Q.; Zhang, K.; Zhao, Q.; Wong, T. W.; Wong, J. W.; Li, T. Thermoset light-responsive biopolyester composite with intrinsic permanent shape reconfigurability and degradability. Macromolecules 2025 , 58 , 1357−1366..

Pilate, F.; Mincheva, R.; De Winter, J.; Gerbaux, P.; Wu, L.; Todd, R.; Raquez, J. M.; Dubois, P. Design of multistimuli-responsive shape-memory polymer materials by reactive extrusion. Chem. Mater. 2014 , 26 , 5860−5867..

Wu, P.; Yu, T.; Chen, M.; Kang, N.; EI Mansori, M. Electrically/magnetically dual-driven shape memory composites fabricated by multi-material magnetic field-assisted 4D printing. Adv. Funct. Mater. 2024 , 34 , 2314854..

Li, Z.; Davidson-Rozenfeld, G.; Vázquez-González, M.; Fadeev, M.; Zhang, J.; Tian, H.; Willner, I. Multi-triggered supramolecular DNA/bipyridinium dithienylethene hydrogels driven by light, re dox, and chemical stimuli for shape-memory and self-healing applications. J. Am. Chem. Soc. 2018 , 140 , 17691−17701..

Hu, J.; Zhu, Y.; Huang, H.; Lu, J. Recent advances in shape–memory polymers: Structure, mechanism, functionality, modeling and applications. Prog. Polym. Sci. 2012 , 37 , 1720−1763..

[Zhao, Q.; Qi, H. J.; Xie, T. Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding. Prog. Polym. Sci . 2015 , 49 − 50 , 79−120..

Delaey, J.; Dubruel, P.; Van Vlierberghe, S. Shape-memory polymers for biomedical applications. Adv. Funct. Mater. 2020 , 30 , 1909047..

Xuan, H.; Guan, Q.; Tan, H.; Zuo, H.; Sun, L.; Guo, Y.; Zhang, L.; Neisiany, R. E.; You, Z. Light-controlled triple-shape-memory, high-permittivity dynamic elastomer for wearable multifunctional information encoding devices. ACS Nano 2022 , 16 , 16954−16965..

Wang, J.; Tu, Z.; Zhang, H.; Wang, M. M.; Liu, W.; Qu, J. P. Ac tuation mechanisms of a semicrystalline elastomer-based polymer artificial muscle with high actuation strain. Macromolecules 2022 , 55 , 3986−3999..

Li, F.; Liu, Y.; Leng, J. Progress of shape memory polymers and their composites in aerospace applications. Smart Mater. Struct. 2019 , 28 , 103003..

de Alencar Lira, M. C.; da Cunha,R. B.; Agrawal, P.; de Figueiredo Brito, G.; de Mélo, T. J. A. Shape memory effect in supertough PETG/EGMA thermoplastic vulcanizates obtained through dynamic vulcanization and interfacial compatibilization. Macromolecules 2024 , 57 , 7315−7330..

[Jiang, Y.; Leng, Q. Y.; Yan, Y.; Ng, E. L. L.; Chee, H. L.; Wang, F.; Chan, S. Y.; Loh, X. J.; Wang, J.; Chan, B. Q. Y. 4D printing of single-network shape memory polyurethanes with two-way actuation properties. ACS Appl. Polym. Mater . 2022 , 4 , 8574−8583..

Murcia, A. P.; Gomez, J. M. U.; Sommer, J. U.; Ionov, L. Two-way shape memory polymers: Evolution of stress vs evolution of elongation. Macromolecules 2021 , 54 , 5838−5847..

Chung, T.; Romo-Uribe, A.; Mather, P. T. Two-way reversible shape memory in a semicrystalline network. Macromolecules 2008 , 41 , 184−192..

Ding, A.; Tang, F.; Alsberg, E. The emerging 4D printing of shape-memory thermomorphs for self-adaptative biomedical implants. Adv. Funct. Mater. 2025 , 35 , 2418348..

Li, Y.; Tang, H. H.; Luo, Y. C.; Huang, Y. T.; Zhu, M.; Zhang, Y. M.; Luo, M. J.; Fan, L. F.; Gan, F.; Ma, C. P.; Chi, Z. Reversible stepless multiple shape memory polymer comprising amorphous region as switching phase. Adv. Funct. Mater. 2025 , 35 , 2500230..

Chen, S.; Hu, J.; Zhuo, H. Properties and mechanism of two-way shape memory polyurethane composites. Compos. Sci. Technol. 2010 , 70 , 1437−1443..

Yang, G.; Li, H.; Xing, R.; Lv, M.; Ma, C.; Yan, J.; Zhuang, X. Thermal-triggered “On-Off” switchable triboelectric nanogenerator based on two-way shape memory polymer. Adv. Funct. Mater. 2023 , 33 , 2214001..

Wang, Z.; Si, M.; Han, J.; Shen, Y.; Yin, G.; Yin, K.; Xiao, P.; Chen, T. Hydrogen-bonded supramolecular network enabled gentle reprogramming of liquid crystal elastomer toward evolutionary robot. Angew. Chem. Int. Ed. 2025 , 64 , e202416095..

Yao, Y.; Wilborn, A. M.; Lemaire, B.; Trigka, F.; Stricker, F.; Weible, A. H.; Li, S.; Bennett, R. K. A.; Cheung, T. C.; Grinthal, A.; Zhernenkov, M.; Freychet, G.; Wąsik, P.; Kozinsky, B.; Lerch, M. M.; Wang, X.; Aizenberg, J. Programming liquid crystal elastomers for multistep ambidirectional deformability. Science 2024 , 386 , 1161−1168..

[Shi, Y.; Fang, G.; Cao, Z.; Shi, F.; Zhao, Q.; Fang, Z.; Xie, T. Digital light fabrication of reversible shape memory polymers. Chem. Eng. J . 2021 , 426 , 131306..

Inverardi, N.; Toselli, M.; Scalet, G.; Messori, M.; Auricchio, F.; Pandini, S. Stress-free two-way shape memory effect of poly(ethylene glycol)/poly( ε -caprolactone) semicrystalline networks. Macromolecules 2022 , 55 , 8533−8547..

Zhou, J.; Turner, S. A.; Brosnan, S. M.; Li, Q.; Carrillo, J. M. Y.; Nykypanchuk, D.; Gang, O.; Ashby, V. S.; Dobrynin, A. V.; She iko, S. S. Shapeshifting: reversible shape memory in semicrystalline elastomers. Macromolecules 2014 , 47 , 1768−1776..

Huang, Y.; Dang, G.; Zhu, M.; Fan, L.; Rong, M.; Zhang, M. External stress-free reversible multiple shape memory polymer enabled by using broad melting range as equivalent multiple switching phases. Appl. Mater. Today 2023 , 30 , 101709..

Uto, K.; Matsushita, Y.; Ebara, M. Multiphase PCL semi-interpenetrating networks exhibiting the triple- and stress-free two-way shape memory effect. Polym. Chem. 2023 , 14 , 1478−1487..

Song, H.; Fang, Z.; Jin, B.; Pan, P.; Zhao, Q.; Xie, T. Synergetic chemical and physical programming for reversible shape memory effect in a dynamic covalent network with two crystalline phases. ACS Macro Lett. 2019 , 8 , 682−686..

Wang, K.; Jia, Y. G.; Zhu, X. X. Two-way reversible shape memory polymers made of cross-linked cocrystallizable random copolymers with tunable actuation temperatures. Macromolecules 2017 , 50 , 8570−8579..

Ren, S.; F eng, J. Reconfigurable and reprocessable thermadapt stress-free two-way shape memory polymers based on a dual crosslinking network with outstanding mechanical properties. Adv. Mater. Technol. 2023 , 8 , 2300029..

Zhang, W.; Zou, C.; Pan, Q.; Hu, G.; Shi, H.; Zhang, Y.; He, X.; He, Y.; Zhang, X. A triple shape memory material of trans-polyisoprene/polycaprolactone with customizable response temperature controlled by crosslinking density. Adv. Funct. Mater. 2024 , 34 , 2400245..

Xu, Z. Y.; Li, L.; Shi, L. Y.; Yang, K. K.; Wang, Y. Z. Effect of self-nucleation and stress-induced crystallization on the tunable two-way shape-memory effect of a semicrystalline network. Macromolecules 2022 , 55 , 5104−5114..

Sabahi, N.; Roohani, I.; Wang, C. H.; Farajzadeh, E.; Li, X. Thermoplastic polyurethane-based shape memory polymers with potential biomedical application: the effect of TPU soft-segment on shape memory effect and cytocompatibility. Polymer 2023 , 283 , 126189..

Yu, G.; Chen, H.; Wang, W.; Zhou, Y.; Zhang, J.; Li, Y. Influence of sepiolite on crystallinity of soft segments and shape memory properties of polyurethane nanocomposites. Polym. Compos. 2018 , 39 , 1674−1681..

Wang, M. H.; Yang, F.; Zhang, Y. J. Tunable thermo-responsive shape memory materials enabled by poly(ε-caprolactone)-poly(2-vinyl)ethylene glycol copolymers via facile thiol-ene photo-crosslink. Chinese J. Polym. Sci. 2025 , 43 , 278−288..

Yuan, W.; Liu, K.; Zhou, J.; Ni, L.; Shan, G.; Bao, Y.; Pan, P. Stress-free two-way shape memory effects of semicrystalline polymer networks enhanced by self-nucleated crystallization. ACS Macro Lett. 2020 , 9 , 1325−1331..

Wang, J.; Zhang, H.; Lei, J.; Wu, M.; Liu, W.; Qu, J. P. Stress-free two-way shape-memory mechanism of a semicrystalline network with a broad melting transition. Macromolecules 2022 , 55 , 10113−10123..

Alvarado-Tenorio, B.; Romo-Uribe, A.; Mather, P. T. Microstructure and phase behavior of POSS/PCL shape memory nanocomposites. Macromolecules 2011 , 44 , 5682−5692..

Borsacchi, S.; Paderni, K.; Messori, M.; Toselli, M.; Pilati, F.; Geppi, M. Insights into shape-memory poly( ε -caprolactone) materials by solid-stat e NMR. Macromolecules 2014 , 47 , 3544−3552..

Tantisuwanno, C.; Jain, T.; Tseng, Y. M.; Joy, A. Pendant amines in the hard or soft segments of PCL-polyurethanes have contrasting effects on the mechanical and surface properties. Macromolecules 2024 , 57 , 4448−4459..

Rueda-Larraz, L.; d’Arlas, B. F.; Tercjak, A.; Ribes, A.; Mondragon, I.; Eceiza, A. Synthesis and microstructure-mechanical property relationships of segmented polyurethanes based on a PCL-PTHF-PCL block copolymer as soft segment. Eur. Polym. J. 2009 , 45 , 2096−2109..

Barańska, H.; Kuduk-Jaworska, J.; Szostak, R.; Romaniewska, A. Vibrational spectra of racemic and enantiomeric malic acids. J. Raman Spectrosc. 2003 , 34 , 68−76..

Li, J.; Rodgers, W. R.; Xie, T. Semi-crystalline two-way shape memory elastomer. Polymer 2011 , 52 , 5320−5325..

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Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid

Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid

DOI：10.1007/s10118-026-3686-6

摘要

Abstract

关键词

Keywords

references