Enhanced Toughness of Poly(<italic style="font-style: italic">L</italic>-lactide)/Poly(<italic style="font-style: italic">ε</italic>-caprolactone) Blends <italic style="font-style: italic">via</italic> Stereocomplex Crystallites: Role of Poly(<italic style="font-style: italic">D</italic>-lactide) Chain Length in Compatibilizers

Lei Gong; Jian-Gang Zhang; Wen Cao; Xiong Liu; Zi-Jun Zhang; Hong-Tao Lu; Jian-Na Bao; Wen-Xing Chen

doi:10.1007/s10118-026-3834-z

Your Location：

Home >

Browse articles >

Enhanced Toughness of Poly(L-lactide)/Poly(ε-caprolactone) Blends via Stereocomplex Crystallites: Role of Poly(D-lactide) Chain Length in Compatibilizers

RESEARCH ARTICLE | Updated：2026-10-28

- Enhanced Toughness of Poly(L-lactide)/Poly(ε-caprolactone) Blends via Stereocomplex Crystallites: Role of Poly(D-lactide) Chain Length in Compatibilizers
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-18(2026)
- Affiliations：
  
  a.School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
  b.Yangzhou Huitong Technology Co., Ltd., Yangzhou 225101, China
- Author bio：
  
  baojianna@zstu.edu.cn
- Funds：
- DOI：10.1007/s10118-026-3834-z
  CLC：
- Received：10 June 2026，
  
  Accepted：04 August 2026，
  
  Online First：28 October 2026，
  
  Published：2026-09
- Accepted：
Scan QR Code
Gong, L.; Zhang, J. G.; Cao, W.; Liu, X.; Zhang, Z. J.; Lu, H. T.; Bao, J. N.; Chen, W. X. Enhanced toughness of poly(L-lactide)/poly(ε-caprolactone) blends via stereocomplex crystallites: role of poly(D-lactide) chain length in compatibilizers. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3834-z

Lei Gong, Jian-Gang Zhang, Wen Cao, et al. Enhanced Toughness of Poly(L-lactide)/Poly(ε-caprolactone) Blends via Stereocomplex Crystallites: Role of Poly(D-lactide) Chain Length in Compatibilizers[J/OL]. Chinese Journal of Polymer Science, 2026, 441-18. DOI: 10.1007/s10118-026-3834-z.
Gong, L.; Zhang, J. G.; Cao, W.; Liu, X.; Zhang, Z. J.; Lu, H. T.; Bao, J. N.; Chen, W. X. Enhanced toughness of poly(L-lactide)/poly(ε-caprolactone) blends via stereocomplex crystallites: role of poly(D-lactide) chain length in compatibilizers. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3834-z DOI：

Lei Gong, Jian-Gang Zhang, Wen Cao, et al. Enhanced Toughness of Poly(L-lactide)/Poly(ε-caprolactone) Blends via Stereocomplex Crystallites: Role of Poly(D-lactide) Chain Length in Compatibilizers[J/OL]. Chinese Journal of Polymer Science, 2026, 441-18. DOI: 10.1007/s10118-026-3834-z. DOI：

摘要

Abstract

Biodegradable poly(

-lactide) (PLLA)/poly(

-caprolactone) (PCL) blends exhibit poor toughness because of their incompatibility. In this study

double-graft polymers (DCL) with different molecular weights of poly(

-lactide) (PDLA) were successfully synthesized through grafting PDLA and PCL onto the multifunctional epoxy-based styrene-acrylic oligomer (ADR) molecular chain by reactive blending

and their structures were confirmed by FTIR and

H-NMR spectra. Based on contact angle measurements and interfacial tension calculations

the graft copolymers preferentially localized at the interface between the two phases. This interfacial arrangement enhanced the interactions across the blend. The incorporation of PDLA was found to induce the formation of stereocomplex (SC) crystallites

which markedly reinforced the interfacial adhesion within the PLLA/PCL blend. Consequently

the elongation at break of the compatibilized blends exhibited an increasing trend with increasing compatibilizer content. Among them

the PLLA/PCL blend containing 5 wt% DCL with PDLA segments of 20 kg/mol exhibited the best tensile performance

outperforming the corresponding blend containing the double-graft copolymer with PLLA segments (LCL) owing to the formation of SC crystallites. Meanwhile

the influences of PDLA in DCL with varying

designed

on the morphology

crystallization

mechanical

thermal

and rheological properties of PLLA/PCL blends were investigated. It was found that DCL with a moderate length of PDLA (

e.g.

designed

=20 kg/mol) displayed better compatibilization efficiency than copolymers with shorter or longer PDLA chains

significantly reducing the size of PCL domains and improving the dispersion uniformity. After incorporating DCL with the PDLA of

designed

=20 kg/mol

the elongation at break and fracture energy of the PLLA/PCL blends reached 304% and 9.7 kJ/m

respectively

which were 20 and 24 times higher than those of the original PLLA/PCL. Compared to the uncompatibilized blend

the compatibilized blends displayed denser spherulites

which were derived from the nucleation of SC crystallization. The mechanical properties of the blends were improved through the transformation of the size and dispersion of PCL domains

and the size of spherulites tuned by PDLA with different molecular weights. By adjusting the molecular weight of PDLA in the compatibilizer

this study offers a strategy for fabricating PLLA-based materials with outstanding toughness.

关键词

Keywords

references

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

Nagarajan, V.; Mohanty, A. K.; Misra, M. Perspective on polylactic acid (PLA) based sustainable materials for durable applications: focus on toughness and heat resistance. ACS Sustainable Chem. Eng. 2016 , 4 , 2899−2916..

Bao, Y. Hydrothermal aging behaviors of CMR/PLA biocomposites. J. Thermoplast. Compos. Mater. 2018 , 31 , 1341−1351..

Bai, H.; Huang, C.; Xiu, H.; Gao, Y.; Zhang, Q.; Fu, Q. Toughening of poly(l-lactide) with poly( ε -caprolactone): combined effects of matrix crystallization and impact modifier particle size. Polymer 2013 , 54 , 5257−5266..

Tokiwa, Y.; Calabia, B. P.; Ugwu, C. U.; Aiba, S. Biodegradability of plastics. Int. J. Mol. Sci. 2009 , 10 , 3722−3742..

Matta, A. K.; Rao, R. U.; Suman, K. N. S.; Rambabu, V. Preparation and characterization of biodegradable PLA/PCL polymeric blends. Procedia Mater. Sci. 2014 , 6 , 1266−1270..

Nofar, M.; Sacligil, D.; Carreau, P. J.; Kamal, M. R.; Heuzey, M. C. Poly(lactic acid) blends: processing, properties and applications. Int. J. Biol. Macromol. 2019 , 125 , 307−360..

Taib, R. M.; Ghaleb, Z. A.; Mohd Ishak, Z. A. Thermal, mechanical, and morphological properties of polylactic acid toughened with an impact modifier. J. Appl. Polym. Sci. 2012 , 123 , 2715−2725..

Yin, H. Y.; Wei, X. F.; Bao, R. Y.; Dong, Q. X.; Liu, Z. Y.; Yang, W.; Xie, B. H.; Yang, M. B. Enhancing thermomechanical properties and heat distortion resistance of poly(l-lactide) with high crystallinity under high cooling rate. ACS Sustainable Chem. Eng. 2015 , 3 , 654−661..

Zhao, T. H.; Yuan, W. Q.; Li, Y. D.; Weng, Y. X.; Zeng, J. B. Relating chemical structure to toughness via morphology control in fully sustainable sebacic acid cured epoxidized soybean oil toughened polylactide blends. Macromolecules 2018 , 51 , 2027−2037..

Liu, Z.; Hu, D.; Huang, L.; Li, W.; Tian, J.; Lu, L.; Zhou, C. Simultaneous improvement in toughness, strength and biocompatibility of poly(lactic acid) with polyhedral oligomeric silsesquioxane. Chem. Eng. J. 2018 , 346 , 649−661..

Yang, Y.; Zhang, L.; Xiong, Z.; Tang, Z.; Zhang, R.; Zhu, J. Research progress in the heat resistance, toughening and filling modification of PLA. Sci. China Chem. 2016 , 59 , 1355−1368..

Jia, S.; Zhao, L.; Wang, X.; Chen, Y.; Pan, H.; Han, L.; Zhang, H.; Dong, L.; Zhang, H. Poly(lactic acid) blends with excellent low temperature toughness: a comparative study on poly(lactic acid) blends with different toughening agents. Int. J. Biol. Macromol. 2022 , 201 , 662−675..

Fang, H.; Jiang, F.; Wu, Q.; Ding, Y.; Wang, Z. Supertough polylactide materials prepared through in situ reactive blending with PEG-based diacrylate monomer. ACS Appl. Mater. Interfaces 2014 , 6 , 13552−13563..

Fang, H.; Wang, S.; Ye, W.; Chen, X.; Wang, X.; Xu, P.; Li, X.; Ding, Y. Simultaneous improvement of mechanical properties and electromagnetic interference shielding performance in eco-friendly polylactide composites via reactive blending and MWCNTs induced morphological optimization. Compos. Part B Eng. 2019 , 178 , 107452..

Yokohara, T.; Yamaguchi, M. Structure and properties for biomass-based polyester blends of PLA and PBS. Eur. Polym. J. 2008 , 44 , 677−685..

Supthanyakul, R.; Kaabbuathong, N.; Chirachanchai, S. Random poly(butylene succinate- co -lactic acid) as a multi-functional additive for miscibility, toughness, and clarity of PLA/PBS blends. Polymer 2016 , 105 , 1−9..

Zhao, T.; Yu, J.; Pan, H.; Zhao, Y.; Zhang, Q.; Yu, X.; Bian, J.; Han, L.; Zhang, H. Super-tough polylactic acid (PLA)/poly(butylene succinate) (PBS) materials prepared through reactive blending with epoxy-functionalized PMMA-GMA copolymer. Int. J. Biol. Macromol. 2023 , 251 , 126150..

Zhou, W.; Chen, X.; Yang, K.; Fang, H.; Xu, Z.; Ding, Y. Achieving morphological evolution and interfacial enhancement in fully degradable and supertough polylactide/polyurethane elastomer blends by interfacial stereocomplexation. Appl. Surf. Sci. 2022 , 572 , 151393..

Yang, Z. T.; Yang, J. X.; Fan, J. H.; Feng, Y. H.; Huang, Z. X. Preparation of super-toughened poly( L -lactide) composites under elongational flow: a strategy for balancing stiffness and ductility. Compos. Sci. Technol. 2021 , 208 , 108758..

Jiang, L.; Wolcott, M. P.; Zhang, J. Study of biodegradable polylactide/poly(butylene adipate- co -terephthalate) blends. Biomacromolecules 2006 , 7 , 199−207..

Finotti, P. F. M.; Costa, L. C.; Capote, T. S. O.; Scarel-Caminaga, R. M.; Chinelatto, M. A. Immiscible poly(lactic acid)/poly( ε -caprolactone) for temporary implants: compatibility and cytotoxicity. J. Mech. Behav. Biomed. Mater. 2017 , 68 , 155−162..

Sivalingam, G.; Madras, G. Thermal degradation of binary physical mixtures and copolymers of poly( ε -caprolactone), poly(d, l-lactide), poly(glycolide). Polym. Degrad. Stab. 2004 , 84 , 393−398..

[Fortelny, I.; Ujcic, A.; Fambri, L.; Slouf, M. Phase structure, compatibility, and toughness of PLA/PCL blends: a review. Front. Mater . 2019 , 6 , 206..

Maglio, G.; Migliozzi, A.; Palumbo, R.; Immirzi, B.; Volpe, M. G. Compatibilized poly( ε -caprolactone)/poly( L -lactide) blends for biomedical uses. Macromol. Rapid Commun. 1999 , 20 , 236−238..

Chen, K.; Zhou, C.; Ya o, L.; Jing, M.; Liu, C.; Shen, C.; Wang, Y. Phase morphology, rheological behavior and mechanical properties of supertough biobased poly(lactic acid) reactive ternary blends. Int. J. Biol. Macromol. 2023 , 253 , 127079..

Yang, D. D.; Wu, C.; Wu, G.; Chen, S. C.; Wang, Y. Z. Toughening of polylactide with high tensile strength via constructing an integrative physical crosslinking network based on ionic interactions. Macromolecules 2021 , 54 , 291−301..

Ikada, Y.; Jamshidi, K.; Tsuji, H.; Hyon, S. H. Stereocomplex formation between enantiomeric poly(lactides). Macromolecules 1987 , 20 , 904−906..

Tsuji, H. Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications. Macromol. Biosci. 2005 , 5 , 569−597..

Tan, B. H.; Muiruri, J. K.; Li, Z.; He, C. Recent progress in using stereocomplexation for enhancement of thermal and mechanical property of polylactide. ACS Sustainable Chem. Eng. 2016 , 4 , 5370−5391..

Zhang, H.; Bai, H.; Deng, S.; Liu, Z.; Zhang, Q.; Fu, Q. Achieving all-polylactide fibers with significantly enhanced heat resistance and tensile strength via in situ formation of nanofibrilized stereocomplex polylactide. Polymer 2019 , 166 , 13−20..

Tsuji, H.; Ikada, Y. Stereocomplex formation between enantiomeric poly(lactic acid)s. XI. Mechanical properties and morphology of solution-cast films. Polymer 1999 , 40 , 6699−6708..

Ma, P.; Shen, T.; Xu, P.; Dong, W.; Lemstra, P. J.; Chen, M. Superior performance of fully biobased poly(lactide) via stereocomplexation-induced phase separation: structure versus property. ACS Sustainable Chem. Eng. 2015 , 3 , 1470−1478..

Zhang, Z. C.; Sang, Z. H.; Huang, Y. F.; Ru, J. F.; Zhong, G. J.; Ji, X.; Wang, R.; Li, Z. M. Enhanced heat deflection resistance via shear flow-induced stereocomplex crystallization of polylactide systems. ACS Sustainable Chem. Eng. 2017 , 5 , 1692−1703..

Ji, N.; Hu, G.; Li, J.; Ren, J. Influence of poly(lactide) stereocomplexes as nucleating agents on the crystallization behavior of poly(lactide)s. RSC Adv. 2019 , 9 , 6221−6227..

Si, W. J.; Zhang, H.; Li, Y. D.; Huang, C.; Weng, Y. X.; Zeng, J. B. Highly toughened and heat resistant poly(l-lactide)/poly( ε -caprolactone) blends via engineering balance between kinetics and thermodynamics of phasic morphology with stereocomplex crystallite. Compos. Part B Eng. 2020 , 197 , 108155..

Rathi, S. R.; Coughlin, E. B.; Hsu, S. L.; Golub, C. S.; Ling, G. H.; Tzivanis, M. J. Effect of midblock on the morphology and properties of blends of ABA triblock copolymers of PDLA-mid-block-PDLA with PLLA. Polymer 2012 , 53 , 3008−3016..

Rahman, N.; Kawai, T.; Matsuba, G.; Nishida, K.; Kanaya, T.; Watanabe, H.; Okamoto, H.; Kato, M.; Usuki, A.; Matsuda, M.; Nakajima, K.; Honma, N. Effect of polylactide stereocomplex on the crystallization behavior of poly(l-lactic acid). Macromolecules 2009 , 42 , 4739−4745..

Yamane, H.; Sasai, K. Effect of the addition of poly(d-lactic acid) on the thermal property of poly(l-lactic acid). Polymer 2003 , 44 , 2569−2575..

Lv, T.; Li, J.; Liu, L.; Huang, S.; Li, H.; Jiang, S. Effects of molecular weight on stereocomplex and crystallization of PLLA/PDLA blends. Polymer 2023 , 283 , 126259..

Yan, C.; Hou, D. F.; Zhang, K.; Yang, M. B. Effects of PDLA molecular weight on the crystallization behaviors and rheological properties of asymmetric PDLA/PLLA blends. Polymer 2023 , 270 , 125764..

Dai, J.; Bai, H.; Liu, Z.; Chen, L.; Zhang, Q.; Fu, Q. Stereocomplex crystallites induce simultaneous enhancement in impact toughness and heat resistance of injection-molded polylactide/polyurethane blends. RSC Adv. 2016 , 6 , 17008−17015..

Liu, Z.; Luo, Y.; Bai, H.; Zhang, Q.; Fu, Q. Remarkably enhanced impact toughness and heat resistance of poly(l-lactide)/thermoplastic polyurethane blends by constructing stereocomplex crystallites in the matrix. ACS Sustainable Chem. Eng. 2016 , 4 , 111−120..

Zeng, Z.; Luo, Y.; Bai, H.; Zhang, Q.; Fu, Q. Manipulating matrix crystallization and impact toughness of polylactide/elastomer blends via tailoring size and packing density of stereocomplex crystallites formed at the interface. Macromol. Mater. Eng. 2022 , 307 , 2100698..

Luo, Y.; Ju, Y.; Bai, H.; Liu, Z.; Zhang, Q.; Fu, Q. Tailor-made dispersion and distribution of stereocomplex crystallites in poly(l-lactide)/elastomer blends toward largely enhanced crystallization rate and impact toughness. J. Phys. Chem. B 2017 , 121 , 6271−6279..

Wu, B.; Zeng, Q.; Niu, D.; Yang, W.; Dong, W.; Chen, M.; Ma, P. Design of supertoughened and heat-resistant PLLA/elastomer blends by controlling the distribution of stereocomplex crystallites and the morphology. Macromolecules 2019 , 52 , 1092−1103..

Deng, S.; Yao, J.; Bai, H.; Xiu, H.; Zhang, Q.; Fu, Q. A generalizable strategy toward highly tough and heat-resistant stereocomplex-type polylactide/elastomer blends with substantially enhanced melt processability. Polymer 2021 , 224 , 123736..

Al-Itry, R.; Lamnawar, K.; Maazouz, A. Improvement of thermal stability, rheological and mechanical properties of PLA, PBAT and their blends by reactive extrusion with functionalized epoxy. Polym. Degrad. Stab. 2012 , 97 , 1898−1914..

Liu, H.; Zhang, J. Research progress in toughening modification of poly(lactic acid). J. Polym. Sci. Part B Polym. Phys. 2011 , 49 , 1051−1083..

Han, Y.; Ning, N.; Wang, Z.; Zhang, L. A new strategy for the preparation of fully biobased and biodegradable polylactic acid with both high rigidity and flexibility. Macromolecules 2024 , 57 , 9216−9229..

Ahmadi, H.; van Heugten, P. M. H.; Veber, A.; Puskar, L.; Anderson, P. D.; Cardinaels, R. Toughening immiscible polymer blends: the role of interface-crystallization-induced compatibilization explored through nanoscale visualization. ACS Appl. Mater. Interfaces 2024 , 16 , 59174−59187..

Fernández-Tena, A.; Otaegi, I.; Irusta, L.; Sebastián, V.; Guerrica-Echevarria, G.; Müller, A. J.; Aranburu, N. High-impact PLA in compatibilized PLA/PCL blends: optimization of blend composition and type and content of compatibilizer. Macromol. Mater. Eng. 2023 , 308 , 2300213..

Yamane, H.; Sasai, K.; Takano, M.; Takahashi, M. Poly( D -lactic acid) as a rheological modifier of poly( L -lactic acid): shear and biaxial extensional flow behavior. J. Rheol. 2004 , 48 , 599−609..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

COMBINED EFFECT OF MODIFIED ZEOLITE 13X AND β-NUCLEATING AGENT ON IMPROVING β-CRYSTAL CONTENT AND TOUGHENING POLYPROPYLENE RANDOM COPOLYMER

Phase Structure Formed by Rubber and Rigid Particles in a Polymer and Its Effect on the Composite Rigidity and Toughness

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

Molecular Conformation and Crystallization Behavior of Bifuran-based Polyesters

Multifunctional Polyurethane with High Strength, Toughness, and Self-healing Capacity via Tannic Acid-modified Cellulose Nanocrystals

Related Author

Jin-hua Leng

Heng Liu

Bo-bing He

Bin Yang

Xian Chen

Qing-quan Qin

Zong-Lin Jiang

Hang-Hang Qi

Related Institution

Polymer Physics and Chemistry, College of Chemistry, Sichuan University

Chengdu Product Quality Supervision and Inspection Institute

Kaixian Chenjia Middle School

College of Materials Science and Engineering, State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Key Laboratory of Textile Fiber and Products of Ministry of Education, Wuhan Textile University

School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology

⁰

Enhanced Toughness of Poly(L-lactide)/Poly(ε-caprolactone) Blends via Stereocomplex Crystallites: Role of Poly(D-lactide) Chain Length in Compatibilizers

DOI：10.1007/s10118-026-3834-z

摘要

Abstract

关键词

Keywords

references