Rapid Stereocomplexation between Enantiomeric Comb-Shaped Cellulose‑g‑poly(l‑lactide) Nanohybrids and Poly(d‑lactide) from the Melt

• Published in: Biomacromolecules 2015-11, Vol.16 (11), p.3723-3729
• Main Authors: Ma, Piming, Jiang, Long, Xu, Pengwu, Dong, Weifu, Chen, Mingqing, Lemstra, Piet J
• Format: Article
• Language: English
• Subjects: Biocompatible Materials - chemistry; Calorimetry, Differential Scanning; Cellulose - chemistry; Crystallization; Half-Life; Microscopy, Atomic Force; Molecular Weight; Nanostructures - chemistry; Polyesters - chemistry; Spectroscopy, Fourier Transform Infrared; Stereoisomerism; X-Ray Diffraction
• ISSN: 1525-7797; 1526-4602
• DOI: 10.1021/acs.biomac.5b01135

In this work we report the in situ preparation of fully biobased stereocomplex poly­(lactide) (SC-PLA) nanocomposites grafted onto nanocrystalline cellulose (NCC). The stereocomplexation rate by compounding high-molar-mass poly­(d-lactide) (PDLA) with comb-like NCC grafted poly­(l-lactide) is rather high in comparison with mixtures of PDLA and PLLA. The rapid stereocomplexation was evidenced by a high stereocomplexation temperature (T c‑sc = 145 °C) and a high SC crystallinity (X c‑sc = 38%) upon fast cooling (50 °C/min) from the melt (250 °C for 2 min), which are higher than currently reported values. Moreover, the half-life crystallization time (175–190 °C) of the SC-PLA was shortened by 84–92% in comparison with the PDLA/PLLA blends. The high­(er) stereocomplexation rate and the melt stability of the SC in the nanocomposites were ascribed to the nucleation effect of the chemically bonded NCC and the “memory effect” of molecular pairs in the stereocomplex melt because of the confined freedom of the grafted PLLA chains.