ABSTRACT
The application of poly(lactic acid) (PLA) is limited by its low crystallization rate. Conventional methods to increase crystallization rate usually result in a significant loss of transparency. In this work, a bundled bis-amide organic compound N'-(3-(hydrazinyloxy)benzoyl)-1-naphthohydrazide (HBNA) was used as a nucleator to prepare PLA/HBNA blends with enhanced crystallization, heat resistance and transparency. HBNA dissolves in PLA matrix at high temperature and self-assembles into bundle microcrystals by intermolecular hydrogen bonding at a lower temperature, which induces PLA to form ample spherulites and "shish-kebab-like" structure rapidly. The effects of HBNA assembling behavior and nucleation activity on the PLA properties and the corresponding mechanism are systematically investigated. As a result, the crystallization temperature of PLA increased from 90 °C to 123 °C by adding as low as 0.75 wt% of HBNA, and the half-crystallization time (t1/2) at 135 °C decreased from 31.0 min to 1.5 min. More importantly, the PLA/HBNA maintains good transparency (transmittance > 75 % and haze is ca. 27 %) due to the decreased crystal size, even though the crystallinity of PLA is increased to 40 %, which also led to good heat resistance. The present work is expected to expand the application of PLA in packaging and other fields.
Subject(s)
Amides , Hot Temperature , Crystallization , Polyesters/chemistryABSTRACT
Comb-like nanocrystal cellulose graft poly (d-lactide) (PDLA), i.e., NCC-g-PDLA nanohybrids were synthesized and compounded with poly (l-lactide) (PLLA) and poly (hydroxyalkanoate)s (PHA) to make fully biobased nanocomposites. Surprisingly, the complex viscosity of the PLLA/PHA melts was reduced by more than one order of magnitudes, viz. from 4000 to 100Pas by incorporation of 2-4wt% of the NCC-g-PDLA nanohybrids. Meanwhile, the crystallization of the PLLA component was accelerated by the NCC-g-PDLA nanohybrids due to the strong interaction between PDLA and PLLA macromolecules. The significant reduction in melt viscosity associating with unique core-shell-like microstructures due to the synergetic effect of the NCC-g-PDLA nanohybrids and the PHA would facilitate the preparation of complex-shaped biomass articles and fibers under low(er) pressure and temperatures, which is beyond pure academic interest.
ABSTRACT
The N1,N1'-(ethane-1,2-diyl)bis(N2-phenyloxalamide) (OXA) is a soluble-type nucleator with a dissolving temperature of 230 °C in poly(l-lactic acid) (PLLA) matrix. The effect of thermal history and shear flow on the crystallization behavior of the PLLA/OXA samples was investigated by rheometry, polarized optical microscopy (POM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). The crystallization process of the PLLA/OXA-240 sample (i.e., pre-melted at 240 °C) was significantly promoted by applying a shear flow, e.g., the onset crystallization time (tonset) of the PLLA at 155 °C was reduced from 1600 to 200 s after shearing at 0.4 rad/s for even as short as 1.0 s, while the crystallinity (Xc) was increased to 40%. Moreover, the tonset of the PLLA/OXA-240 sample is 60%â»80% lower than that of the PLLA/OXA-200 sample (i.e., pre-melted at 200 °C) with a total shear angle of 2 rad, indicating a much higher crystallization rate of the PLLA/OXA-240 sample. A better organization and uniformity of OXA fibrils can be obtained due to a complete pre-dissolution in the PLLA matrix followed by shear and oscillation treatments. The well dispersed OXA fibrils and flow-induced chain orientation are mainly responsible for the fast crystallization of the PLLA/OXA-240 samples. In addition, the shear flow created some disordered α'-form crystals in the PLLA/OXA samples regardless of the thermal history (200 or 240 °C).