期刊
POLYMER DEGRADATION AND STABILITY
卷 195, 期 -, 页码 -出版社
ELSEVIER SCI LTD
DOI: 10.1016/j.polymdegradstab.2021.109803
关键词
Aromatic polyesters; Enantiomeric polyesters; Crystallization; Stereocomplex; Thermal degradation; Thermal properties
资金
- Hibi Science Foundation
- JSPS KAKENHI [16K05912]
This study investigated enantiomeric aromatic poly(lactic acid)s and their crystallization, thermal properties, and degradation. It was found that high molecular weight poly(L-mandelic acid) and poly(d-mandelic acid) exhibited predominant stereocomplex crystallization, while low molecular weight blends showed both stereocomplex and homo-crystallization. The aromatic poly(mandelic acid) had higher glass transition temperatures and lower melting temperatures compared to previously reported poly(lactic acid)s. The thermal degradation temperatures of the blends were higher than those of enantiomeric poly(lactic acid)s and similar to enantiomeric poly(2-hydroxybutanoic acid)s. The study also compared the crystallizability of aromatic poly(mandelic acid) and poly(phenyllactic acid).
Enantiomeric aromatic poly(lactic acid)s, i.e., poly(L-mandelic acid) (PLMA) and poly(d-mandelic acid) (PDMA), with different number-average molecular weight (M-n) values were synthesized by polycondensation and their stereocomplex (SC) crystallization and homo-crystallization by solvent-evaporation, as well as thermal properties and degradation were investigated in detail. The SC crystallization was confirmed by wide-angle X-ray diffraction and differential scanning calorimetry. However, Fourier-transfer infrared spectroscopy could not identify SC crystallization, excluding the lowered peak width of the carbonyl group. Predominant SC crystallization was observed for high molecular weight PLMA/PDMA (M-n = 1.7 x 10(4) and 1.5 x 10(4) g mol(-1), respectively) blends and low molecular weight PLMA/PDMA (M-n = 5.8 x 103 and 7.2 x 10(3) g mol(-1)) blends, except for low molecular weight PLMA/PDMA blend with a PLMA fraction of 75%, where both SC crystallization and homo-crystallization occurred. This can be explained by the lower crystallizability of homo-crystallites at high Mn values compared to that of SC crystallites. The glass transition temperatures of poly(mandelic acid)s (87 degrees C - 112 degrees C) were higher than those previously reported for poly(lactic acid)s (PLAs) (approximately 60 degrees C), poly(2-hydroxybutanoic acid)s [P(2HB)s] (24 degrees C - 44 degrees C), and poly(phenyllactic acid) (32 degrees C - 47 degrees C). In marked contrast with the results previously reported for enantiomeric PLAs and P(2HB)s, melting temperatures of SC crystallites of PMAs (105 degrees C - 127 degrees C) were lower than those of homo-crystallites (162 degrees C - 180 degrees C). The thermal degradation temperatures at 10% weight loss for unblended PLMA, PDMA, and their (50/50) blend (290 degrees C - 313 degrees C) were much higher than those reported for unblended enantiomeric PLAs, and their (50/50) blend (218 degrees C - 243 degrees C) and similar to those reported for enantiomeric P(2HB)s, and their (50/50) blend (300 degrees C - 330 degrees C). The thermal degradation profiles and temperatures of unblended PLMA, PDMA, and their blend were similar with each other, whereas the activation energy for thermal degradation (Delta E-td) of PLMA/PDMA blend (136.7- 163.0 kJ mol(-1)) was between those of unblended PLMA (117.7 - 154.4 kJ mol(-1)) and unblended PDMA (196.3 - 226.6 kJ mol(-1)). These results contrast with those previously reported for enantiomeric PLAs and P(2HB)s, wherein Delta E-td values were increased by enantiomeric polymer blending. Furthermore, the crystallizability of aromatic poly(mandelic acid) and poly(phenyllactic acid) was compared. (C) 2021 Elsevier Ltd. All rights reserved.
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