Crystallization and solid-state structure of random polylactide copolymers: Poly(L-lactide-co-D-lactide)s

S. Baratian, E. S. Hall, J. S. Lin, R. Xu, James Patrick Runt

Research output: Contribution to journalArticle

118 Citations (Scopus)

Abstract

This paper presents a continuation of our earlier research on the crystallization and solid-state structure of polylactide copolymers. The focus here is on random copolymers containing predominately L-lactide and small amounts (1.5, 3, and 6%) of D-lactide. As expected, degrees of crystallinity and spherulite growth rates decrease substantially with increasing D-lactide content in the copolymers. The importance of defect arrangement (isolated vs paired stereochemical defects) was demonstrated by comparison to our earlier research on L-lactide/meso-lactide copolymers. At a given degree of supercooling, measured lamellar thicknesses decrease significantly with increasing R stereoisomer concentration: e.g., by more than a factor of 2 (compared to poly(L-lactide)) for the 6% D-lactide copolymer. The results of small-angle X-ray scattering experiments indicate that a significant amount of noncrystalline material resides between lamellar stacks. Equilibrium melting points were estimated for the copolymers using the Gibbs-Thomson approach, and the values conform with predictions of the model of Wendling and Surer in the exclusion limit. Taken together with the significant reduction in lamellar thickness and crystallinity, these results point to substantial rejection of D-lactide (and meso-lactide) defects from S stereoisomer crystals. However, experiments by others on similar copolymers suggest that a significant amount of R (or R-R) isomers can be included in S crystals under certain crystallization conditions. Some speculation about the origin of these differences is presented.

Original languageEnglish (US)
Pages (from-to)4857-4864
Number of pages8
JournalMacromolecules
Volume34
Issue number14
DOIs
StatePublished - Jul 3 2001

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Crystallization
Copolymers
Stereoisomerism
Defects
Supercooling
Crystals
poly(lactide)
dilactide
X ray scattering
Isomers
Melting point
Experiments

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Baratian, S. ; Hall, E. S. ; Lin, J. S. ; Xu, R. ; Runt, James Patrick. / Crystallization and solid-state structure of random polylactide copolymers : Poly(L-lactide-co-D-lactide)s. In: Macromolecules. 2001 ; Vol. 34, No. 14. pp. 4857-4864.
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Crystallization and solid-state structure of random polylactide copolymers : Poly(L-lactide-co-D-lactide)s. / Baratian, S.; Hall, E. S.; Lin, J. S.; Xu, R.; Runt, James Patrick.

In: Macromolecules, Vol. 34, No. 14, 03.07.2001, p. 4857-4864.

Research output: Contribution to journalArticle

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T1 - Crystallization and solid-state structure of random polylactide copolymers

T2 - Poly(L-lactide-co-D-lactide)s

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AU - Runt, James Patrick

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AB - This paper presents a continuation of our earlier research on the crystallization and solid-state structure of polylactide copolymers. The focus here is on random copolymers containing predominately L-lactide and small amounts (1.5, 3, and 6%) of D-lactide. As expected, degrees of crystallinity and spherulite growth rates decrease substantially with increasing D-lactide content in the copolymers. The importance of defect arrangement (isolated vs paired stereochemical defects) was demonstrated by comparison to our earlier research on L-lactide/meso-lactide copolymers. At a given degree of supercooling, measured lamellar thicknesses decrease significantly with increasing R stereoisomer concentration: e.g., by more than a factor of 2 (compared to poly(L-lactide)) for the 6% D-lactide copolymer. The results of small-angle X-ray scattering experiments indicate that a significant amount of noncrystalline material resides between lamellar stacks. Equilibrium melting points were estimated for the copolymers using the Gibbs-Thomson approach, and the values conform with predictions of the model of Wendling and Surer in the exclusion limit. Taken together with the significant reduction in lamellar thickness and crystallinity, these results point to substantial rejection of D-lactide (and meso-lactide) defects from S stereoisomer crystals. However, experiments by others on similar copolymers suggest that a significant amount of R (or R-R) isomers can be included in S crystals under certain crystallization conditions. Some speculation about the origin of these differences is presented.

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