Hydrolytic degradation studies of bio-composites of poly(L-lactic acid)/Oligo(L-lactic acid) grafted and non-grafted microcrystalline cellulose

Md. Hafezur Rahaman , Abu Rayhan , G.M. Arifuzzaman Khan , Md. Ashraful Alam , S.M. Nur Alam , Md. Tauhidul Islam , Md. Aminur Rahman
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Abstract

This study investigates the hydrolytic degradation properties of poly(L-lactic acid) (PLLA)- based biodegradable polymer composites which were prepared with oligo(L-lactic acid) (OLLA) grafted and non-grafted microcrystalline cellulose (MCC) (OLLA-g-MCC and Non-g-MCC). MCC was obtained through the simple hydrolysis reaction of cellulose and then it was grafted with OLLA. The grafted MCC was characterized by FTIR, SEM and WAXD analyses. Composite of PLLA with OLLA-g-MCC (PLLA/OLLA-g-MCC) and Non-g-MCC (PLLA/Non-g-MCC) were prepared using the solution casting method. The hydrolytic degradation properties of composite samples were tested in a buffer solution at pH 7.4 and 37 °C. The changes in samples after degradation were monitored by analyzing the mechanical properties: thermal stability, crystallinity, degradability and making a comparison with that of PLLA. Both OLLA-g-MCC and Non-g-MCC enhanced the hydrolytic degradation of PLLA, which was observed by evaluating weight loss percentage. The initial weight loss rates of PLLA/OLLA-g-MCC (0.22 % day−1) and PLLA/Non-g-MCC (0.27 % day−1) were higher than that of PLLA (0.12 % day−1). The hydrolysis phenomenon is comparatively linear (Regression coefficient 0.9693) for PLLA, whereas nonlinearity is shown in the case of PLLA/Non-g-MCC composite. The PLLA/OLLA-g-MCC exhibits a higher Ke than that of PLLA/Non-g-MCC and PLLA. The decline in pH indicates the generation of acidic substances. DSC shows that the degradation temperature of hydrolytically degraded samples declined sharply with hydrolytic degradation time up to 130 days and then the rate slowed down. Initial rapid increase in crystallinity was observed which may due to segmental mobility during hydrolytic degradation of the composites and polymer.
聚乳酸/低聚乳酸接枝和非接枝微晶纤维素生物复合材料的水解降解研究
研究了低聚l -乳酸(OLLA)接枝和非接枝微晶纤维素(OLLA-g-MCC和Non-g-MCC)制备的聚l -乳酸(PLLA)基可生物降解聚合物复合材料的水解降解性能。通过纤维素的简单水解反应得到MCC,然后与OLLA接枝。通过FTIR、SEM和WAXD对接枝的MCC进行了表征。采用溶液铸造法制备了PLLA与OLLA-g-MCC的复合材料(PLLA/OLLA-g-MCC)和Non-g-MCC (PLLA/Non-g-MCC)。在pH 7.4和37℃的缓冲溶液中测试复合材料样品的水解降解性能。通过分析其热稳定性、结晶度、可降解性等力学性能,并与PLLA进行对比,监测降解后样品的变化。OLLA-g-MCC和Non-g-MCC均促进了PLLA的水解降解,这是通过评价失重率来观察的。PLLA/OLLA-g-MCC的初始失重率(0.22 % day−1)和PLLA/Non-g-MCC的初始失重率(0.27 % day−1)高于PLLA(0.12 % day−1)。PLLA的水解现象是相对线性的(回归系数为0.9693),而PLLA/Non-g-MCC复合材料的水解现象是非线性的。PLLA/OLLA-g-MCC的Ke值高于PLLA/Non-g-MCC和PLLA。pH值的下降表明酸性物质的产生。DSC表明,水解降解样品的降解温度急剧下降,水解降解时间可达130 d,随后降解速度减慢。观察到结晶度最初的快速增加,这可能是由于复合材料和聚合物在水解降解过程中的节段迁移。
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