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  • Review Article
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Tacticity-independent crystallization of polymers

Nature Chemistry volume 18, pages 625–638 (2026) Cite this article

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Abstract

Crystallization, a phase transition that is prevalent in nature, provides unique molecular arrangements that impact the structure-dependent properties of a material. Owing to thermodynamic and kinetic factors, synthetic polymeric materials show only partial ordering. Indeed, usually polymers that possess sufficient stereo- and regioregularity can partially crystallize. Atactic polymers that do not meet the minimum regularity in the chemical structure needed to pack chains within a crystal unit cell are completely amorphous. However, there are unusual cases where stereoirregular, atactic polymers can crystallize; this happens when the structural features of the atactic polymers provide specific ordering so that their irregular chains can pack into crystalline structures. This Review not only highlights the general relationship between the structures required in atactic polymers to induce crystallization but also provides researchers with the tools to design polymer systems with crystallinity without requiring exquisite stereocontrol in their synthesis.

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Fig. 1: Overview of crystalline materials in nature and in human-made materials.
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Fig. 2: Summary of the factors that induce crystallization in atactic polymers.
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Fig. 3: Overview of atactic semicrystalline polymers containing hydrogen bonds.
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Fig. 4: Overview of atactic semicrystalline polymers containing dipolar interactions.
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Fig. 5: Overview of semicrystalline polymers with conformational flexibility.
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Fig. 6: Overview of atactic semicrystalline polymers with steric effects.
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Acknowledgements

L.S., A.S., M.X., H.S. and A.J.M. acknowledge support from the following projects: the María de Maeztu Excellence Unit CEX2023-001303-M funded by MCIN/AEI/10.13039/501100011033; PID2023-149734NB-C22 funded by MCIN/AEI/10.13039/501100011033, TED2021-129852B-C22 funded by MCIN/AEI/10.13039/501100011033 and PID2022-138199NB-I00 funded by MCIN/AEI/10.13039/501100011033; the Basque Country Government, GC IT 1667-22; and Universidad del País Vasco UPV/EHU, EHU-N24/54. M.X. acknowledges the Gipuzkoa Fellows Programme from the Provincial Council of Gipuzkoa, grant G75067454. L.S. thanks the Gipuzkoa Fellows Programme from the Provincial Council of Gipuzkoa, grant 2024-FELL-000010. L.S. also acknowledges the fellowship from the “la Caixa” Foundation (ID 100010434) (code B006525). M.S. and C.D.R. acknowledge financial support from the project PRIN-PNRR 2022 (grant no. P2022N9T7X) of the Ministry of University of Italy “Polymers of tunable molecular structure and properties from bio-renewable sources designed for a complete chemical recycling to monomers (Re-Tune)”. E.Y.-X.C. acknowledges support by the US National Science Foundation (NSF-2305058). The work by C.S. was supported by the BOTTLE Consortium funded by the US Department of Energy via the National Laboratory of the Rockies under Contract DE-AC36-08GO28308. The funders had no role in the study design, data collection and analysis, decision to publish or preparation of the manuscript.

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Authors and Affiliations

  1. POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain

    Leire Sangroniz, Ainara Sangroniz, Marta Ximenis, Haritz Sardon & Alejandro J. Müller

  2. Department of Chemistry, Colorado State University, Fort Collins, CO, USA

    Changxia Shi & Eugene Y.-X. Chen

  3. Beijing National Laboratory for Molecular Sciences, Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Changxia Shi

  4. Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Naples, Italy

    Miriam Scoti & Claudio De Rosa

  5. IKERBASQUE, Basque Foundation for Science, Bilbao, Spain

    Alejandro J. Müller

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  1. Leire Sangroniz
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All authors contributed to discussions and the writing of the manuscript.

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Correspondence to Claudio De Rosa, Eugene Y.-X. Chen, Haritz Sardon or Alejandro J. Müller.

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Sangroniz, L., Sangroniz, A., Shi, C. et al. Tacticity-independent crystallization of polymers. Nat. Chem. 18, 625–638 (2026). https://doi.org/10.1038/s41557-026-02113-w

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