Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

Extended-chain crystallization and stereocomplex formation of polylactides in a Langmuir monolayer

Polymer Journal volume 52, pages 601–613 (2020)Cite this article

Subjects

Abstract

Polylactide (PLA) forms an extended-chain crystal (ECC) in a Langmuir monolayer. Therefore, the chain packings in crystals can be identified by simply evaluating the crystal sizes. Initially, we confirmed ECC formation and found that the lamella thicknesses were proportional to the molecular weight, although they were ~80% of the thickness expected for the chain conformation. Atomic force microscopy images indicated that the chains were tilted counterclockwise and clockwise for poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), respectively, in the lamella and that the length along the chain direction was in good agreement with the length expected for the chain conformation. A mixture of a high-molecular-weight (HMW) PDLA and a low-molecular-weight (LMW) PDLA was found to crystallize sequentially to form macroscopically separated crystals, although the individual crystalline behavior was almost the same according to the surface pressure–area isotherms. Furthermore, we studied the stereocomplex (SC) formation and found that the SC also formed as an extended-chain SC (ECSC), molecular structure of which was successfully visualized. A mixture of an HMW-PLLA and an LMW-PDLA was found to form an SC, the size of which was determined by the extended LMW-PDLA chains, and the HMW-PLLA chains were predicted to be folded and packed in the SC.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Auras R, Lim L-T, Selke SEM, Tsuji H, editors. Poly(lactic acid): Synthesis, Structures, Properties, Processing, and Applications (Wiley Series on Polymer Engineering and Technology). New Jersey: John Wiley & Sons. Inc.; 2010.

  2. Ikada Y, Jamshidi K, Tsuji H, Hyon S-H. Stereocomplex formation between enantiomeric poly(lactides). Macromolecules. 1987;20:904–6.

    Article  CAS  Google Scholar 

  3. Tsuji H. Poly(lactic acid) stereocomplexes: a decade of progress. Adv Drug Deliv Rev. 2016;107:97–135.

    Article  CAS  Google Scholar 

  4. Ni S, Yin W, Ferguson-McPherson MK, Satija SK, Morris JR, Esker AR. Nanoscale surface patterns from 103 single molecule helices of biodegradable poly(L-lactic acid). Langmuir. 2006;22:5969–73.

    Article  CAS  Google Scholar 

  5. Ni S, Lee W, Li B, Esker AR. Thermodynamics of the liquid expanded to condensed phase transition of Poly(L-lactic acid) in Langmuir monolayers. Langmuir. 2006;22:3672–7.

    Article  CAS  Google Scholar 

  6. Bourque H, Laurin I, Pézolet M, Klass JM, Lennox RB, Brown GR. Investigation of the poly(L-lactide)/poly(D-lactide) stereocomplex at the air–water interface by polarization modulation infrared reflection absorption spectroscopy. Langmuir. 2001;17:5842–9.

    Article  CAS  Google Scholar 

  7. Klass JM, Lennox RB, Brown GR, Bourque H, PĂ©zolet M. Enantiomeric polylactides at the air–water interface: π–A isotherms and PM-IRRAS studies of enantiomers and their blend. Langmuir. 2003;19:333–40.

    Article  CAS  Google Scholar 

  8. Pelletier I, Pézolet M. Compression-induced stereocomplexation of polylactides at the air/water interface. Macromolecules. 2004;37:4967–73.

    Article  CAS  Google Scholar 

  9. Lee W-K, Iwata T, Gardella JJA. Hydrolytic behavior of enantiomeric poly(lactide) mixed monolayer films at the air/water interface: stereocomplexation effects. Langmuir. 2005;21:11180–4.

    Article  CAS  Google Scholar 

  10. Duan Y, Liu J, Sato H, Zhang J, Tsuji H, Ozaki Y, et al. Molecular weight dependence of the Poly(L-lactide)/Poly(D-lactide) stereocomplex at the air-water interface. Biomacromolecules. 2006;7:2728–35.

    Article  CAS  Google Scholar 

  11. Kim YS, Snively CM, Liu Y, Rabolt JF, Chase DB. Real-time imaging of crystallization in polylactide enantiomeric monolayers at the air–water interface. Langmuir. 2008;24:10791–6.

    Article  CAS  Google Scholar 

  12. Sasaki S, Asakura T. Helix distortion and crystal structure of the α-form of Poly(L-lactide). Macromolecules. 2003;36:8385–90.

    Article  CAS  Google Scholar 

  13. Wasanasuk K, Tashiro K, Hanesaka M, Ohhara T, Kurihara K, Kuroki R, et al. Crystal structure analysis of Poly(L-lactic acid) α form on the basis of the 2-dimensional wide-angle synchrotron X-ray and neutron diffraction measurements. Macromolecules. 2011;44:6441–52.

    Article  CAS  Google Scholar 

  14. Bassett DC, Frank FC, Keller A. Some new habit features in crystals of long chain compounds. III. Direct observations on unflattened monolayer polyethylene crystals. Philos Mag. 1963;8:1753–87.

    Article  CAS  Google Scholar 

  15. Unger G, Zeng X-b. Learning polymer crystallization with the aid of linear, branched and cyclic model compounds. Chem Rev. 2001;101:4157–88.

    Article  Google Scholar 

  16. de Silva DS, Zeng X-b, Unger G, Spells SJ. On perpendicular and tilted chains in lamellar crystals. J Macromol Sci B. 2003;42:915–27.

    Article  Google Scholar 

  17. Wang H-F, Chiang C-H, Hsu W-C, Wen T, Chuang W-T, Lotz B, et al. Handedness of twisted lamella in banded spherulite of chiral polylactides and their blends. Macromolecules. 2017;50:5466–75.

    Article  CAS  Google Scholar 

  18. Wang E-D, Ruan J, Huang Y-F, Su A-C. Stem tilt in the contact plane of epitaxially grown polylactide lamellae and its direct correlation with lamellar bending. Macromolecules. 2011;44:4335–41.

    Article  CAS  Google Scholar 

  19. Okihara T, Tsuji M, Kawaguchi A, Takayama K-I. Crystal structure of stereocomplex of poly(L-lactide) and poly(D-lactide). J Macromol Sci Phys B. 1991;30:119–40.

    Article  CAS  Google Scholar 

  20. Kumaki J, Kawauchi T, Yashima E. Two-dimensional folded chain crystals of a synthetic polymer in a Langmuir–Blodgett film. J Am Chem Soc. 2005;127:5788–9.

    Article  CAS  Google Scholar 

  21. Takanashi Y, Kumaki J. Significant melting point depression of two-dimensional folded-chain crystals of isotactic poly(methyl methacrylate)s observed by high-resolution in situ atomic force microscopy. J Phys Chem B. 2013;117:5605.

    Article  Google Scholar 

  22. Kumaki J, Kawauchi T, Okoshi K, Kusanagi H, Yashima E. Supramolecular helical structure of the stereocomplex composed of complementary isotactic and syndiotactic poly(methyl methacrylate)s as revealed by atomic force microscopy. Angew Chem Int Ed. 2007;46:5348–51.

    Article  CAS  Google Scholar 

  23. Kumaki J, Kawauchi T, Ute K, Kitayama T, Yashima E. Molecular weight recognition in the multiple-stranded helix of a synthetic polymer without specific monomer–monomer interaction. J Am Chem Soc. 2008;130:6373–80.

    Article  CAS  Google Scholar 

  24. Kumaki J, Sakurai S-I, Yashima E. Visualization of synthetic helical polymers by high-resolution atomic force microscopy. Chem Soc Rev. 2009;38:737–46.

    Article  CAS  Google Scholar 

  25. Kumaki J. Observation of polymer chain structures in two-dimensional films by atomic force microscopy. Polym J. 2016;48:3–14.

    Article  CAS  Google Scholar 

  26. Chen W, Wang S, Zhang W, Ke Y, Hong Y-l, Miyoshi T. Molecular structural basis for stereocomplex formation of polylactide enantiomers in dilute solution. ACS Macro Lett. 2015;4:1264–7.

    Article  CAS  Google Scholar 

  27. Wang S, Yuan S, Chen W, He Q, Hong Y-l, Miyoshi T, et al. Study of the chain trajectory and crystallization mechanism of poly(L-lactic acid) in dilute solution. Macromolecules. 2017;50:6404–14.

    Article  CAS  Google Scholar 

  28. Wang S, Yuan S, Chen W, Zhou Y, Hong Y-l, Miyoshi T. Structual unit of polymer crystallization in dilute solution AS studied by solid-state NMR and 13C isotope labeling. Macromolecules. 2018;51:8729–37.

    Article  CAS  Google Scholar 

  29. Wang S, Yuan S, Wang K, Chen W, Yamada K, Barkley D, et al. Intermolecular and intermolecular packing in polymer crystallization. Macromolecules. 2019;52:4739–48.

    Article  CAS  Google Scholar 

  30. de Gennes P-G. Scaling concepts in polymer physics. Ithaca: Cornell University Press; 1979. p. 61.

Download references

Acknowledgements

This work was supported by JSPS KAKENHI Grant Numbers 20106009, 21350059, 23655208, and 18H02025.

Author information

Author notes

  1. Kenji Watanabe

    Present address: Battery Division, Toshiba Corporation, 8 Shinsugita-cho, Isogo-ku Yokohama-shi, Kanagawa, 235-8522, Japan

Authors and Affiliations

  1. Department of Polymer Science and Engineering, Graduate School of Science and Engineering, Yamagata University, Yonezawa, Yamagata, 992-8510, Japan

    Kenji Watanabe

  2. Department of Organic Materials Science, Graduate School of Organic Materials Science, Yamagata University, Yonezawa, Yamagata, 992-8510, Japan

    Jiro Kumaki

Authors
  1. Kenji Watanabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiro Kumaki
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jiro Kumaki.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Watanabe, K., Kumaki, J. Extended-chain crystallization and stereocomplex formation of polylactides in a Langmuir monolayer. Polym J 52, 601–613 (2020). https://doi.org/10.1038/s41428-020-0312-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-020-0312-2

Search

Advanced search

Quick links