Compounding and Melt Strengthening of Poly(Lactic Acid): Shear and Elongation Rheological Investigations for Forming Process

Abstract:

The poly (lactic acid) (PLA), through its organic origin and its biodegradation properties, can be a good alternative to petroleum-based polymers. To this end, the forming process as well blown extrusion and foaming of PLA was investigated in this study as an alternative for the production of food packaging. Through this work, we present some promising routes to enhance its processing ability which presents several challenges mainly due to the poor shear and elongation properties of this biopolymer. To our knowledge, there is no paper dedicated to the investigation of foaming and/or blown extrusion of PLA that involves structural, rheological and thermo-mechanical properties. To achieve this objective, various formulations of PLA with multifunctionalized epoxy, nucleants and plasticizer were prepared and characterized on the basis of their linear viscoelasticity and extensional properties. The balance of chain extension and branching has been also investigated using solution viscosimetry, Steric exclusion chromatography (SEC) and rheology (relaxation spectrum, Van Gurp Palmen curves….). We pushed further by characterizing both the structure and thermo-mechanical properties of PLA formulations. On one hand, a batch foaming assisted with supercritical CO2 was achieved following a full characterization in physicochemical, rheological and thermal domain, The influence of the foaming parameters, the extent of chain modification as well as the contribution of crystallization on cell morphology was evaluated. Based on these parameters, structures ranging from micro to macro-cellular-cell were obtained. On the other hand, the stability maps of blown processing for neat and modified PLA were established at different die temperatures. We have achieved a great enhancement of the blown processing windows of PLA with high BUR (Blow Up Ratio) and TUR (Take Up Ratio) attained. We were able to demonstrate that a higher kinetic of crystallization can also be reached for chain-extended and branched PLA formulated with adequate amounts of nucleants and plasticizers. Induced crystallization during process was also demonstrated. Through this work, blown films with interesting thermo-mechanical and mechanical properties have been produced using an optimal formulation for PLA. References [1] A. Maazouz, K. Lamnawar, B. Mallet, Patent: C08L67/00; C08J5/10. FR2941702 (A1). (2010) [2] Y.-M. Corre, A. Maazouz, J. Duchet, J. Reignier, Batch foaming of chain extended PLA with supercritical CO2: Influence of the rheological properties and the process parameters on the cellular structure. J. of Supercritical Fluids,58 (2011) 177-188 [3] B. Mallet, K. Lamnawar, A. Maazouz, Compounding and processing of biodegradable materials based on PLA for packaging applications: In greening the 21st century material’s world, Frontiers in Science and Engineering, 1-2(2011) 1-44 [4] B. Mallet, K. Lamnawar, A. Maazouz, Improvement of blown extrusion processing of PLA: structure-processing-properties relashionships. Polymer engineering and Science (To appear in 2013).

• Periodical: Key Engineering Materials (Volumes 554-557)
• Pages: 1751-1756
• DOI: https://doi.org/10.4028/www.scientific.net/KEM.554-557.1751
• Online since: June 2013
• Authors: Benoit Mallet, Khalid Lamnawar, Abderrahim Maazouz
• Keywords: Blown Processing, Chain Branching, Chain Extension, Forming Process, Poly(lactic acid) (PLA), Rheology

References

[1] M. Vert, G. Schwarch, J. Coudane, Present and future of PLA polymers. J. Macromol. Sci., Part A. Pure Appl. Chem. 32(1995) 787-796.

DOI: 10.1080/10601329508010289

[2] J. Lunt, Large-scale production, properties and commercial applications of polylactic acid polymers. Polym. Degrad. Stabil. 59 (1998) 145-152.

DOI: 10.1016/s0141-3910(97)00148-1

[3] R. H. Wehrenberg, Lactic acid polymers: strong, degradable thermoplastics. Mater. Eng.94 (1981) 63-66.

[4] R. E. Drumright, P. R. Gruber, D. E. Henton, Polylactic Acid Technology. Adv. Mater. 12 (2000) 1841 - 1846.

DOI: 10.1002/1521-4095(200012)12:23<1841::aid-adma1841>3.0.co;2-e

[5] E.S. Lipinsky, R. G. Sinclair, Is lactic acid a commodity chemical? Chem. Eng. Prog. 82(1986) 26–32.

[6] J. R. Dorgan, J. S. Williams, D.N. Lewis, Melt rheology of poly(lactic acid): Entanglement and chain architecture effects. J. Rheol.43 (1999) 1141-1155.

DOI: 10.1122/1.551041

[7] Z. F. Zhou, G. Q. Huang, W. B. Xu, F. M. Ren, Chain extension and branching of poly(L-lactic acid) produced by reaction with a DGEBA-based epoxy resin. eXPRESS Polym. Lett. 1 (2007) 734–739.

DOI: 10.3144/expresspolymlett.2007.101

[8] A.L. Arraiza, J.R. Sarasua, J. Verdu, X. Colin, Rheological behavior and modeling of thermal degradation of poly(e-caprolactone) and poly(L-Lactide). Polymer processing XXII 5(2007) 389-394.

DOI: 10.3139/217.2067

[9] J. D. Campbell, , J. A. Debling, D. J. DeYoung, I. Giannakitsas, D. R. Hellwig, D. D. Schatz, F. Teymour, M. A. Villalobos, Process for producing polymers by free radical polymerization and condensation reaction, and apparatus and products related thereto. U.S. Patent 6, 346, 590. (2002).

[10] M. Villalobos, A. Awojulu, T. Greeley, G. Turco, G. Deeter, Oligomeric chain extenders for economic reprocessing and recycling of condensation plastics. Energy 31(2006) 3227–3234.

DOI: 10.1016/j.energy.2006.03.026

[11] Y.-M. Corre, A. Maazouz, J. Duchet, J. Reignier, Batch foaming of chain extended PLA with supercritical CO2: Influence of the rheological properties and the process parameters on the cellular structure. J. of Supercritical Fluids58(2011) 177– 188.

DOI: 10.1016/j.supflu.2011.03.006

[12] A. Maazouz, K. Lamnawar, B. Mallet, F.R. Patent 2941702 (A1), (2010)

[13] B. Mallet, K. Lamnawar, A. Maazouz,Compounding and processing of biodegradable materials based on PLA for packaging applications: In greening the 21st century material's world, Frontiers in Science and Engineering, 1-2(2011) 1-44

[14] B. Mallet, K. Lamnawar, A. Maazouz, Improvement of blown extrusion processing of PLA: structure-processing-properties relashionships. Polymer engineering and Science (To appear 2013).

DOI: 10.1002/pen.23610