Stereocomplex crystallization and homo-crystallization of star-shaped four-armed stereo diblock poly(lactide)s during precipitation and non-isothermal crystallization

Tsuji, Hideto; Matsumura, Nobutsugu; Arakawa, Yuki

doi:10.1038/pj.2016.73

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Published: 31 August 2016

Biopolymers, Bio-related Polymer Materials

Stereocomplex crystallization and homo-crystallization of star-shaped four-armed stereo diblock poly(lactide)s during precipitation and non-isothermal crystallization

Hideto Tsuji¹,
Nobutsugu Matsumura¹ &
Yuki Arakawa¹

Polymer Journal volume 48, pages 1087–1093 (2016)Cite this article

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Poly(L-lactide) (PLLA) is a biobased biodegradable polyester that can be used in various applications, such as commodity, industrial, biomedical, pharmaceutical and environmental applications.¹ The stereocomplexed materials from enantiomeric PLLA and poly(D-lactide) (PDLA) have attracted much attention as advanced poly(lactide) (PLA)-based materials because of their superior mechanical performance as well as the hydrolytic/thermal degradation resistance of stereocomplexed PLA materials compared with that of conventional PLA-based materials.^{2, 3, 4} Stereocomplex (SC)-crystallization in enantiomeric polymer blends containing both linear one-armed PLLA and PDLA (1-L and 1-D, respectively)^{2, 3, 4, 5, 6, 7, 8} and linear one-armed stereoblock copolymers^{2, 3, 4, 9, 10, 11, 12} has been extensively studied. Stereoblock copolymerization is effective at facilitating SC-crystallization because PLLA and PDLA blocks are next to each other. The effects of the star-shaped or branching architecture on SC-crystallization were investigated using blends of both multiarmed PLLA and PDLA,¹³ blends of 1-L and multiarmed PDLA and multiarmed PLLA and 1-D¹⁴ and miktoarmed PLLA and PDLA.¹⁵ A star-shaped or branching architecture disturbs the SC-crystallization.

Similar to linear one-armed stereoblock PLA,¹¹ only SC-crystallites were formed in star-shaped four-armed stereo diblock equimolar PLA (4-LD) polymers.¹⁶ In the present article as well as in previous articles, ‘equimolar’ means that a polymer contains the same amounts of L- and D-lactyl units. Recently, stereo diblock copolymers of PLA polymers with different arm numbers and high molecular weights were synthesized, and their isothermal and non-isothermal crystallization was investigated.¹⁷ The melting temperature, degree of crystallinity, spherulitic growth rate, crystallite size, long period and crystalline layer thickness of stereo diblock copolymers of PLA polymers decreased with increasing branch number owing to the retarding effect of branching on the crystallization rate and crystallizability. In previous studies,^{16, 18} we investigated the static isothermal crystallization of star-shaped 4-LD polymers with different molecular weights or different L-lactyl unit contents as well as a star-shaped 4-L polymer from the melt. Only SC-crystallites were formed in 4-LD in a L-lactyl unit range from 31% to 72%. Both branching and diblock architectures disturbed the SC-crystallization and spherulite growth of equimolar 4-LD polymers, and the effect of the disturbance was larger for branching architectures than for diblock architectures. However, the branching architecture primarily hindered the simultaneous formation of SC- and homo-crystallites of non-equimolar 4-LD polymers.

References

Slager, J. & Domb, A. J. Biopolymer stereocomplexes. Adv. Drug Deliv. Rev. 55, 549–583 (2003).
Article CAS Google Scholar
Tsuji, H. Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications. Macromol. Biosci. 5, 569–597 (2005).
Article CAS Google Scholar
Tsuji, H. Poly(lactic acid) stereocomplexes: a progress of decade. Adv. Drug Del. Rev. doi:10.1016/j.addr.2016.04.017 (in press)
Tsuji, H., Ikada, Y., Hyon, S. H., Kimura, Y. & Kitao, T. Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid). J. Appl. Polym. Sci. 51, 337–344 (1994).
Article CAS Google Scholar
Serizawa, T., Yamashita, H, Fujiwara, T., Kimura, Y. & Akashi, M. Stepwise assembly of enantiomeric poly(lactide)s on surfaces. Macromolecules 34, 1996–2001 (2001).
Article CAS Google Scholar
Takasaki, M., Ito, H. & Kikutani, T. Development of stereocomplex crystal of polylactide in high-speed melt spinning and subsequent drawing and annealing processes. J. Macromol. Sci. Phys. 42B (3-4 SPEC.), 403–420 (2003).
Article Google Scholar
Fujita, M., Sawayanagi, T., Abe, H., Tanaka, T., Iwata, T., Ito, K., Fujisawa, T. & Maeda, M. Stereocomplex formation through reorganization of poly(L-lactic acid) and poly(D-lactic acid) crystals. Macromolecules 41, 2852–2858 (2008).
Article CAS Google Scholar
Ishii, D., Ying, T. H., Mahara, A., Murakami, S., Yamaoka, T., Lee, W. & Iwata, T. In vivo tissue response and degradation behavior of PLLA and stereocomplexed PLA nanofibers. Biomacromolecules 10, 237–242 (2009).
Article CAS Google Scholar
Li, L., Zhong, Z., De Jeu, W. H., Dijkstra, P. J. & Feijen, J. Crystal structure and morphology of poly(L-lactide-b-D-lactide) diblock copolymers. Macromolecules 37, 8641–8646 (2004).
Article CAS Google Scholar
Sugai, N., Yamamoto, T. & Tezuka, Y. Synthesis of orientationally isomeric cyclic stereoblock polylactides with head-to-head and head-to-tail linkages of the enantiomeric segments. ACS Macro Lett. 1, 902–906 (2012).
Article CAS Google Scholar
Tsuji, H., Wada, T., Sakamoto, Y. & Sugiura, Y. Stereocomplex crystallization and spherulite growth behavior of poly(L-lactide)-b-poly(D-lactide) stereodiblock copolymers. Polymer 51, 4937–4947 (2010).
Article CAS Google Scholar
Masutani, K., Lee, C. W. & Kimura, Y. Synthesis and properties of stereo di- and tri-block polylactides of different block compositions by terminal diels-alder coupling of poly-L-lactide and poly-D-lactide prepolymers. Polym. J. 45, 427–435 (2013).
Article CAS Google Scholar
Sakamoto, Y. & Tsuji, H. Stereocomplex crystallization behavior and physical properties of linear 1-arm, 2-arm, and branched 4-arm poly(L-lactide)/poly(D-lactide) blends: effects of chain directional change and branching. Macromol. Chem. Phys. 214, 776–786 (2013).
Article CAS Google Scholar
Shao, J., Sun, J., Bian, X., Cui, Y., Li, G. & Xuesi, C. Investigation of poly(lactide) stereocomplexes: 3-armed poly(L-lactide) blended with linear and 3-armed enantiomers. J. Phys. Chem. B 116, 9983–9991 (2012).
Article CAS Google Scholar
Isono, T., Kondo, Y., Otsuka, I., Nishiyama, Y., Borsali, R., Kakuchi, T. & Satoh, T. Synthesis and stereocomplex formation of star-shaped stereoblock polylactides consisting of poly(L-lactide) and poly(D-lactide) arms. Macromolecules 46, 8509–8518 (2013).
Article CAS Google Scholar
Tsuji, H. & Matsumura, N. Stereocomplex crystallization of star-shaped four-armed stereo diblock poly(lactide)s with different molecular weights: isothermal crystallization from the melt. Macromol. Chem. Phys. 217, 1547–1557 (2006).
Article Google Scholar
Han, L., Shan, G., Bao, Y. & Pan, P. Exclusive stereocomplex crystallization of linear and multiarm star-shaped high-molecular-weight stereo diblock poly(lactic acid)s. J. Phys. Chem. B 119, 14270–14279 (2015).
Article CAS Google Scholar
Tsuji, H., Matsumura, N. & Arakawa, Y. Stereocomplex crystallization and homocrystallization of star-shaped four-armed stereo diblock poly(lactide)s with different L-lactyl unit contents: isothermal crystallization from the melt. J. Phys. Chem. B 120, 1183–1193 (2016).
Article CAS Google Scholar
Gedde U. W. in Polymer Physics Ch. 8, 170–98 (Chapman & Hall, London, UK, 1995)
Tsuji, H., Tamai, K., Kimura, T., Kubota, A., Tahahashi, A., Kuzuya, A. & Ohya, Y. Stereocomplex- and homo-crystallization of blends from 2-armed poly(L-lactide) and poly(D-lactide) with identical and opposite chain directional architectures and of 2-armed stereo diblock poly(lactide). Polymer 96, 167–181 (2016).
Article CAS Google Scholar

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Acknowledgements

This research was supported by JSPS KAKENHI grant number 16K05912 and MEXT KAKENHI grant number 24108005.

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Department of Environmental and Life Sciences, Graduate School of Engineering, Toyohashi University of Technology, Aichi, Japan
Hideto Tsuji, Nobutsugu Matsumura & Yuki Arakawa

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Hideto Tsuji
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Nobutsugu Matsumura
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Correspondence to Hideto Tsuji.

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Tsuji, H., Matsumura, N. & Arakawa, Y. Stereocomplex crystallization and homo-crystallization of star-shaped four-armed stereo diblock poly(lactide)s during precipitation and non-isothermal crystallization. Polym J 48, 1087–1093 (2016). https://doi.org/10.1038/pj.2016.73

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Received: 14 May 2016
Revised: 04 July 2016
Accepted: 04 July 2016
Published: 31 August 2016
Issue date: November 2016
DOI: https://doi.org/10.1038/pj.2016.73

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PLLA and cassava thermoplastic starch blends: crystalinity, mechanical properties, and UV degradation

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