The use of a new bio-based plasticizer derived from epoxidized chia seed oil (ECO) was applied in a poly(lactic acid) (PLA) matrix. ECO was used due to its high epoxy content (6.7%), which led to an improved chemical interaction with PLA. Melt extrusion was used to plasticize PLA with different ECO content in the 0–10 wt.% range. Mechanical, morphological, and thermal characterization was carried out to evaluate the effect of ECO percentage. Besides, disintegration and migration tests were studied to assess the future application in packaging industry. Ductile properties improve by 700% in elongation at break with 10 wt.% ECO content. Field emission scanning electron microscopy (FESEM) showed a phase separation with ECO content equal or higher than 7.5 wt.%. Thermal stabilization was improved 14 °C as ECO content increased. All plasticized PLA was disintegrated under composting conditions, not observing a delay up to 5 wt.% ECO. Migration tests pointed out a very low migration, less than 0.11 wt.%, which is to interest to the packaging industry.
In this study, a novel epoxidized vegetable oil (EVO) from chia seed oil (CSO) has been obtained, with the aim to be employed in a great variety of green products related to the polymeric industry, as plasticizers and compatibilizers. Previous to the epoxidation process characterization, the fatty acid (FA) composition of CSO was analyzed using gas chromatography (GC). Epoxidation of CSO has been performed using peracetic acid formed in situ with hydrogen peroxide and acetic acid, applying sulfuric acid as catalyst. The effects of key parameters as temperature (60, 70, and 75 °C), the molar ratio of hydrogen peroxide:double bond (H2O2:DB) (0.75:1.0 and 1.50:1.0), and reaction time (0–8 h) were evaluated to obtain the highest relative oxirane oxygen yield (Yoo). The evaluation of the epoxidation process was carried out through iodine value (IV), oxirane oxygen content (Oo), epoxy equivalent weight (EEW), and selectivity (S). The main functional groups were identified by means of FTIR and 1H NMR spectroscopy. Physical properties were compared in the different assays. The study of different parameters showed that the best epoxidation conditions were carried out at 75 °C and H2O2:DB (1.50:1), obtaining an Oo value of 8.26% and an EEW of 193 (g·eq−1). These high values, even higher than those obtained for commercial epoxidized oils such as soybean or linseed oil, show the potential of the chemical modification of chia seed oil to be used in the development of biopolymers.
9 February 2023 in Macromolecular Materials and Engineering
Diethyl l‐tartrate (DET) is used as a biobased plasticizer for poly(lactide) (PLA) formulations with improved ductile properties without compromising biodegradation. Different weight percentages (wt.%) of DET in the 0–50 wt.% range are added to PLA by melt compounding and subsequently processed by injection molding. The effect of wt.% DET on mechanical, thermal, thermo‐mechanical, morphology, biodegradation, and crystallinity is studied. Addition of 20 wt.% DET leads to a noticeable increase in elongation at break up to values of 567%, which is quite an interesting result considering the extreme brittleness of PLA. These results are verified by field emission scanning electron microscopy (FESEM) images, where filament‐like structures are observed, indicative of an effective plasticization. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) show that the glass transition temperature of PLA is drastically decreased down to values of 23 °C for the sample with the highest amount of DET (50 wt.%), thus increasing its ductility and processability. Fourier‐transformed infrared spectroscopy (FTIR) spectra show that there exists chemical interactions between PLA and DET. Finally, the biodegradability analysis proves that the developed blends are fully biodegradable, achieving complete disintegration after 49 days. It is observed that DET enhanced the disintegration rate of PLA.
In this study, for the first time, Brazil nut seed oil was chemically modified with maleic anhydride to obtain maleinized Brazil nut seed oil (MBNO). The same process was developed to obtain maleinized hemp seed oil (MHO). The use of MBNO and MHO was studied as bio-based plasticizers by incorporating them with different contents ranging from 0 to 10 phr in a polylactic acid (PLA) matrix. By means of mechanical, thermal and thermomechanical characterization techniques, the properties of the different formulations were studied to evaluate the plasticizing effect of the MBNO and MHO. With the addition of both plasticizers, a significant increase in ductile properties was observed, reaching an increase in elongation at break of 643% with 7.5 phr MBNO and 771% with 10 phr MHO compared to neat PLA. In addition, it has been observed that the mechanical resistant properties do not decrease, since the oils enhance the crystallization of PLA by increasing the free volume between its chains and counteracting the effect. Finally, a disintegration test was carried out under thermophilic conditions at 58 °C for 27 days, demonstrating that the incorporation of MHO and MBNO does not significantly affect the biodegradability of neat PLA.
This work evaluates for the first time the potential of an environmentally friendly plasticizer derived from epoxidized Brazil nut oil (EBNO) for biopolymers, such as poly(lactic acid) (PLA). EBNO was used due to its high epoxy content, reaching an oxirane oxygen content of 4.22% after 8 h of epoxidation for a peroxide/oil ratio of 2:1. Melt extrusion was used to plasticize PLA formulations with different EBNO contents in the range of 0–10 phr. The effects of different amounts of EBNO in the PLA matrix were studied by performing mechanical, thermal, thermomechanical, and morphological characterizations. The tensile test demonstrated the feasibility of EBNO as a plasticizer for PLA by increasing the elongation at break by 70.9% for the plasticized PLA with 7.5 phr of EBNO content in comparison to the unplasticized PLA. The field-emission scanning electron microscopy (FESEM) of the fractured surfaces from the impact tests showed an increase in porosity and roughness in the areas with EBNO addition, which was characteristic of ductile failure. In addition, a disintegration test was performed, and no influence on the PLA biodegradation process was observed. The overall results demonstrate the ability of EBNO to compete with other commercial plasticizers in improving the ductile properties of PLA.
We aimed to study the distribution of hydroxyapatite (HA) and halloysite nanotubes (HNTs) as fillers and their influence on the hydrophobic character of conventional polymers used in the biomedical field. The hydrophobic polyester poly (ε-caprolactone) (PCL) was blended with its more hydrophilic counterpart poly (lactic acid) (PLA) and the hydrophilic acrylate poly (2-hydroxyethyl methacrylate) (PHEMA) was analogously compared to poly (ethyl methacrylate) (PEMA) and its copolymer. The addition of HA and HNTs clearly improve surface wettability in neat samples (PCL and PHEMA), but not that of the corresponding binary blends. Energy-dispersive X-ray spectroscopy mapping analyses show a homogenous distribution of HA with appropriate Ca/P ratios between 1.3 and 2, even on samples that were incubated for seven days in simulated body fluid, with the exception of PHEMA, which is excessively hydrophilic to promote the deposition of salts on its surface. HNTs promote large aggregates on more hydrophilic polymers. The degradation process of the biodegradable polyester PCL blended with PLA, and the addition of HA and HNTs, provide hydrophilic units and decrease the overall crystallinity of PCL. Consequently, after 12 weeks of incubation in phosphate buffered saline the mass loss increases up to 48% and mechanical properties decrease above 60% compared with the PCL/PLA blend.