title: Crystal growth and solid-state structure of poly(lactide) Stereocopolymers.
abstract: Solid-state structure and melting behavior for random stereocopolymers of L-lactide with meso-lactide (P(L-LA-co-meso-LA)) with different meso-LA compositions of 0, 2, 4, and 10 mol % were investigated under various isothermal crystallization conditions. The crystalline morphology of P(L-LA-co-meso-LA) samples changed from the spherulitic aggregates to hexagonal lamellae stacking with a rise in crystallization temperature. Under each crystallization condition, P(L-LA-co-meso-LA) samples formed alpha-crystal modifications for homopolymer of L-LA. By using the atomic force microscopy and small-angle X-ray scattering, the stacking structure of lamellar crystals was examined for the isothermally crystallized P(L-LA-co-meso-LA) thin films. The lamellar thickness of P(L-LA-co-meso-LA) ranged from 6.2 to 15.5 nm, and the values increased with crystallization temperature. Melting profiles of crystalline regions were examined by the differential scanning calorimetry (DSC) for the P(L-LA-co-meso-LA) samples. Distinct two melting peaks were detected in the DSC thermograms of several samples. Investigations on the time-dependent changes in lamellar structure and melting temperature of the P(L-LA-co-meso-LA) samples under isothermal crystallization conditions provided the evidence that a small amount of D-lactyl units was trapped in the crystalline regions during early stage of crystallization process under the certain crystallization condition. In addition, it was found that the D-lactyl units trapped in crystalline regions were excluded from crystalline lamellae to form the thermally stable crystals without changes in crystal thickness during further isothermal storage at a crystallization temperature. The equilibrium melting temperature (T(m)0) of P(L-LA-co-meso-LA) samples was estimated by using modified Hoffman-Weeks methods, and the obtained values decreased from 215 to 184 degrees C as the meso-LA composition was increased from 0 to 10 mol %. Furthermore, the crystal growth kinetics of the P(L-LA-co-meso-LA) samples was analyzed by using the secondary nucleation theory. Transitions of crystalline regime both from regime III to regime II and from regime II to regime I were detected for each sample. The transition temperature from regime II to regime I of each of the P(L-LA-co-meso-LA) samples was very close to the temperature region revealed the morphological changes in the crystalline aggregates from the spherulitic aggregates to hexagonal lamellae stacking.
authors.affiliation: Polymer Chemistry Laboratory, RIKEN Institute, Hirosawa, Wako-shi, Saitama 351-0198, Japan. habe@riken.jp
authors.forename: Hideki
authors.initials: H
authors.lastname: Abe
authors.forename: Mariko
authors.initials: M
authors.lastname: Harigaya
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Kikkawa
authors.forename: Takeharu
authors.initials: T
authors.lastname: Tsuge
authors.forename: Yoshiharu
authors.initials: Y
authors.lastname: Doi
mesh_terms: D002152:Calorimetry, Differential Scanning; D003460:Crystallization; D018360:Crystallography, X-Ray; D018625:Microscopy, Atomic Force; D011091:Polyesters / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D011091:Polyesters; C033616:poly(lactide)