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. 2020 Jun 17;12(6):1366.
doi: 10.3390/polym12061366.

Sustainable Micro and Nano Additives for Controlling the Migration of a Biobased Plasticizer from PLA-Based Flexible Films

Laura Aliotta  1   2 , Alessandro Vannozzi  1   2 , Luca Panariello  1   2 , Vito Gigante  1   2 , Maria-Beatrice Coltelli  1   2 , Andrea Lazzeri  1   2
Affiliations

Sustainable Micro and Nano Additives for Controlling the Migration of a Biobased Plasticizer from PLA-Based Flexible Films

Laura Aliotta et al. Polymers (Basel). .

Abstract

Plasticized poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blend-based films containing chitin nanofibrils (CN) and calcium carbonate were prepared by extrusion and compression molding. On the basis of previous studies, processability was controlled by the use of a few percent of a commercial acrylic copolymer acting as melt strength enhancer and calcium carbonate. Furthermore, acetyl n-tributyl citrate (ATBC), a renewable and biodegradable plasticizer (notoriously adopted in PLA based products) was added to facilitate not only the processability but also to increase the mechanical flexibility and toughness. However, during the storage of these films, a partial loss of plasticizer was observed. The consequence of this is not only correlated to the change of the mechanical properties making the films more rigid but also to the crystallization and development of surficial oiliness. The effect of the addition of calcium carbonate (nanometric and micrometric) and natural nanofibers (chitin nanofibrils) to reduce/control the plasticizer migration was investigated. The prediction of plasticizer migration from the films' core to the external surface was carried out and the diffusion coefficients, obtained by regression of the experimental migration data plotted as the square root of time, were evaluated for different blends compositions. The results of the diffusion coefficients, obtained thanks to migration tests, showed that the CN can slow the plasticizer migration. However, the best result was achieved with micrometric calcium carbonate while nanometric calcium carbonate results were less effective due to favoring of some bio polyesters' chain scission. The use of both micrometric calcium carbonate and CN was counterproductive due to the agglomeration phenomena that were observed.

Keywords: diffusion; plasticizer migration; poly(butylene succinate); poly(lactic acid).

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Examples of diffusion-controlled (blue line) and evaporation-controlled (black line) shape concentration profile.
Figure 2
Figure 2
Concentration profile for all the compositions examined in this paper.
Figure 3
Figure 3
Weight loss percentage as function of the time for (a) F1, F2, F3 and F4 formulations, (b) F4 compared to F5, F6, (c) F4 compared to F7 and F8.
Figure 3
Figure 3
Weight loss percentage as function of the time for (a) F1, F2, F3 and F4 formulations, (b) F4 compared to F5, F6, (c) F4 compared to F7 and F8.
Figure 4
Figure 4
SEM micrographs of F4, F5, F6, F7, and F8 formulations. The F8 micrographs was obtained by backscattered electrons to better evidence CaCO3 particles (white).
Figure 4
Figure 4
SEM micrographs of F4, F5, F6, F7, and F8 formulations. The F8 micrographs was obtained by backscattered electrons to better evidence CaCO3 particles (white).
Figure 5
Figure 5
Comparison between thermograms before and after the migration test (first heating).
Figure 6
Figure 6
Trend of the diffusion coefficient over the time for all the formulation examined.
Figure 7
Figure 7
Comparison between MFR data and D calculated by Equation (6).
Figure 8
Figure 8
First part of the stress-strain curves for the formulations examined.
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