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Crystal Polymorphism and Morphology of Polylactides

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Book cover Synthesis, Structure and Properties of Poly(lactic acid)

Part of the book series: Advances in Polymer Science ((POLYMER,volume 279))

Abstract

The crystal structures of poly(l-lactic acid) (PLLA), its stereocomplexes, and some features of its crystallization process are reviewed. PLLA exists in different crystal modifications that are based on two different left-handed helix geometries having three units in one turn (31) or ten units in three turns (103). The stable α-phase with a 103 helix exists in two variants: an ordered α-phase produced at high crystallization temperature and a less ordered α′-phase produced at low crystallization temperature. Two structures are based on the 31 helical conformation: an elusive γ-phase, obtained so far only by epitaxial crystallization, and a frustrated trigonal β-phase. The β-phase, first obtained in stretched fibers, could be an intermediate or precursor phase of the low crystallization temperature α′-PLLA variant, which would explain a number of its unusual crystallization features (increased growth rate, thicker lamellae, structural disorder). Stereocomplexes of PLLA and poly(d-lactic acid) (PDLA) are formed through intimate association of left- and right-handed threefold helices. They have remarkably higher melting temperatures than the homopolymers, which is explained by the presence of a dense network of weak CH…OC hydrogen bonds. Single crystals of PLLA are obtained both from solution and thin film growth. Spherulites of chiral polylactides are frequently made of twisted lamellae with a large pitch, with the sense of twist depending on the polylactide chirality.

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Notes

  1. 1.

    In this review, PLLA is used as a “generic” designation for the chiral polymers poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) when the chirality distinction is not mandatory.

  2. 2.

    For an extensive list of references see, for example, [18].

  3. 3.

    A parallel can be made with the α- and β-phases of isotactic polypropylene (iPP). The frustrated β-phase growth rate is faster than that of the α-phase in a T c window ranging from about 150 to 100 °C [22]. No crystal–crystal transformation is, however, possible in this case because β-iPP is chiral and α-iPP is made of left- and right-handed helices. A solid-state crystal–crystal transformation would require reversal of helical hand for half of the helices that form the β-iPP crystal.

  4. 4.

    A recent paper [28] considers a lower symmetry space group (P −3) for the form I of iPBu1 than has been used so far. It could therefore also apply for the PLLA/PDLA stereocomplex. However, the differences between the two structures are relatively minor and do not invalidate the argument developed here.

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Authors and Affiliations

  1. Institut Charles Sadron (CNRS and Université de Strasbourg), 23, Rue du Lœss, 67034, Strasbourg, France

    Bernard Lotz

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  1. Bernard Lotz
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Correspondence to Bernard Lotz .

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  1. Composites and Biomaterials, National Research Council, Institute of Polymers, Pozzuoli (NA), Italy

    Maria Laura Di Lorenzo

  2. Interdisciplinary Center for Transfer-Oriented Research in Natural Sciences, Martin Luther University Halle-Wittenberg, Halle/S., Germany

    René Androsch

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Lotz, B. (2017). Crystal Polymorphism and Morphology of Polylactides. In: Di Lorenzo, M., Androsch, R. (eds) Synthesis, Structure and Properties of Poly(lactic acid). Advances in Polymer Science, vol 279. Springer, Cham. https://doi.org/10.1007/12_2016_15

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