[en] Concerning new polylactide (PLA) applications, the study investigates the toughening of PLA-CaSO4 β-anhydrite II (AII) composites with bio-sourced tributyl citrate (TBC). The effects of 5-20 wt.% TBC were evaluated in terms of morphology, mechanical and thermal properties, focusing on the enhancement of PLA crystallization and modification of glass transition temperature (Tg). Due to the strong plasticizing effects of TBC (even at 10%), the plasticized composites are characterized by significant decrease of Tg and rigidity, increase of ductility and impact resistance. Correlated with the amounts of plasticizer, a dramatic drop in melt viscosity is also revealed. Therefore, for applications requiring increased viscosity and enhanced melt strength (extrusion, thermoforming), the reactive modification, with up to 1% epoxy functional styrene-acrylic oligomers, was explored to enhance their rheology. Moreover, larger quantities of products were obtained by reactive extrusion (REX) and characterized to evidence their lower stiffness, enhanced ductility, and toughness. In current prospects, selected samples were tested for the extrusion of tubes (straws) and films. The migration of plasticizer was not noted (at 10% TBC), whereas the mechanical and thermal characterizations of films after two years of aging evidenced a surprising preservation of properties.
Research center :
CIRMAP - Centre d'Innovation et de Recherche en Matériaux Polymères
Disciplines :
Materials science & engineering
Author, co-author :
Murariu, Marius ; Laboratory of Polymeric and Composite Materials, Materia Nova Materials R&D Center & UMons Innovation Center, 3 Avenue Copernic, 7000 Mons, Belgium
Sreekumar K. Bindhu B. Veluraja K. Perspectives of polylactic acid from structure to applications Polym. Renew. Resour. 2021 12 60 74 10.1177/20412479211008773
Murariu M. Dubois P. PLA composites: From production to properties Adv. Drug Deliv. Rev. 2016 107 17 46 10.1016/j.addr.2016.04.003 27085468
Banerjee R. Ray S.S. An overview of the recent advances in polylactide-based sustainable nanocomposites Polym. Eng. Sci. 2021 61 617 649 10.1002/pen.25623
Balla E. Daniilidis V. Karlioti G. Kalamas T. Stefanidou M. Bikiaris N.D. Vlachopoulos A. Koumentakou I. Bikiaris D.N. Poly(lactic acid): A versatile biobased polymer for the future with multifunctional properties—From monomer synthesis, polymerization techniques and molecular weight increase to PLA applications Polymers 2021 13 1822 10.3390/polym13111822 34072917
Teixeira S. Eblagon K.M. Miranda F. Pereira M.F.R. Figueiredo J.L. Towards controlled degradation of poly(lactic) acid in technical applications C 2021 7 42 10.3390/c7020042
Dubois P. Reactive extrusion (rex): Using chemistry and engineering to solve the problem of ocean plastics Engineering 2022 14 15 18 10.1016/j.eng.2021.12.009
Rezvani Ghomi E. Khosravi F. Saedi Ardahaei A. Dai Y. Neisiany R.E. Foroughi F. Wu M. Das O. Ramakrishna S. The life cycle assessment for polylactic acid (PLA) to make it a low-carbon material Polymers 2021 13 1854 10.3390/polym13111854
Vink E.T.H. Davies S. Life cycle inventory and impact assessment data for 2014 Ingeo™ polylactide production Ind. Biotechnol. 2015 11 167 180 10.1089/ind.2015.0003
Widiastuti I. Polylactide nanocomposites for packaging materials: A review AIP Conf. Proc. 2016 1710 030020 10.1063/1.4941486
Kirac F.T. Dagdelen A.F. Saricaoglu F.T. Recent advances in polylactic acid biopolymer films used in food packaging systems J. Food Nutr. Res. 2022 61 1 15
Auras R. Harte B. Selke S. An overview of polylactides as packaging materials Macromol. Biosci. 2004 4 835 864 10.1002/mabi.200400043 15468294
Avinc O. Khoddami A. Overview of Poly(lactic acid) (PLA) fibre Fibre Chem. 2009 41 391 401 10.1007/s10692-010-9213-z
Raquez J.-M. Habibi Y. Murariu M. Dubois P. Polylactide (PLA)-based nanocomposites Prog. Polym. Sci. 2013 38 1504 1542 10.1016/j.progpolymsci.2013.05.014
Van den Oever M. Molenveld K. Replacing fossil based plastic performance products by bio-based plastic products—technical feasibility New Biotechnol. 2017 37 48 59 10.1016/j.nbt.2016.07.007 27445201
Tripathi N. Misra M. Mohanty A.K. Durable polylactic acid (PLA)-based sustainable engineered blends and biocomposites: Recent developments, challenges, and opportunities ACS Eng. Au 2021 1 7 38 10.1021/acsengineeringau.1c00011
Nagarajan V. Mohanty A.K. Misra M. Perspective on polylactic acid (PLA) based sustainable materials for durable applications: Focus on toughness and heat resistance ACS Sustain. Chem. Eng. 2016 4 2899 2916 10.1021/acssuschemeng.6b00321
Masutani K. Kimura Y. Present situation and future perspectives of Poly(lactic acid) Synthesis, Structure and Properties of Poly(lactic acid) Di Lorenzo M.L. Androsch R. Springer International Publishing Cham, Switzerland 2018 1 25
DeStefano V. Khan S. Tabada A. Applications of PLA in modern medicine Eng. Regen. 2020 1 76 87 10.1016/j.engreg.2020.08.002
Wellenreuther C. Wolf A. Zander N. Cost competitiveness of sustainable bioplastic feedstocks—A Monte Carlo analysis for polylactic acid Clean. Eng. Technol. 2022 6 100411 10.1016/j.clet.2022.100411
Nieddu E. Mazzucco L. Gentile P. Benko T. Balbo V. Mandrile R. Ciardelli G. Preparation and biodegradation of clay composites of PLA React. Funct. Polym. 2009 69 371 379 10.1016/j.reactfunctpolym.2009.03.002
Kim H.-S. Park B.H. Choi J.H. Yoon J.-S. Mechanical properties and thermal stability of poly(l-lactide)/calcium carbonate composites J. Appl. Polym. Sci. 2008 109 3087 3092 10.1002/app.28229
Yu W. Wang X. Ferraris E. Zhang J. Melt crystallization of PLA/talc in fused filament fabrication Mater. Des. 2019 182 108013 10.1016/j.matdes.2019.108013
Li H. Huneault M.A. Effect of nucleation and plasticization on the crystallization of poly(lactic acid) Polymer 2007 48 6855 6866 10.1016/j.polymer.2007.09.020
Ge X. Chang M. Jiang W. Zhang B. Xing R. Bulin C. Selective location of kaolin and effects of maleic anhydride in kaolin/poly(ε-caprolactone)/poly(lactic acid) composites Appl. Clay Sci. 2020 189 105524 10.1016/j.clay.2020.105524
Murariu M. Paint Y. Murariu O. Laoutid F. Dubois P. Recent advances in production of ecofriendly polylactide (PLA)-calcium sulfate (anhydrite II) composites: From the evidence of filler stability to the effects of PLA matrix and filling on key properties Polymers 2022 14 2360 10.3390/polym14122360
YousefniaPasha H. Mohtasebi S.S. Tabatabaeekoloor R. Taherimehr M. Javadi A. Soltani Firouz M. Preparation and characterization of the plasticized polylactic acid films produced by the solvent-casting method for food packaging applications J. Food Process. Preserv. 2021 45 e16089 10.1111/jfpp.16089
Zych A. Perotto G. Trojanowska D. Tedeschi G. Bertolacci L. Francini N. Athanassiou A. Super tough polylactic acid plasticized with epoxidized soybean oil methyl ester for flexible food packaging ACS Appl. Polym. Mater. 2021 3 5087 5095 10.1021/acsapm.1c00832
Murariu M. Da Silva Ferreira A. Pluta M. Bonnaud L. Alexandre M. Dubois P. Polylactide (PLA)–CaSO4 composites toughened with low molecular weight and polymeric ester-like plasticizers and related performances Eur. Polym. J. 2008 44 3842 3852 10.1016/j.eurpolymj.2008.07.055
Akindoyo J.O. Beg M.D.H. Ghazali S. Heim H.P. Feldmann M. Impact modified PLA-hydroxyapatite composites—Thermo-mechanical properties Compos. Part A Appl. Sci. Manuf. 2018 107 326 333 10.1016/j.compositesa.2018.01.017
Gigante V. Canesi I. Cinelli P. Coltelli M.B. Lazzeri A. Rubber toughening of polylactic acid (PLA) with poly(butylene adipate-co-terephthalate) (PBAT): Mechanical properties, fracture mechanics and analysis of ductile-to-brittle behavior while varying temperature and test speed Eur. Polym. J. 2019 115 125 137 10.1016/j.eurpolymj.2019.03.015
Zhao X. Hu H. Wang X. Yu X. Zhou W. Peng S. Super tough poly(lactic acid) blends: A comprehensive review RSC Adv. 2020 10 13316 13368 35492128 10.1039/D0RA01801E
Anderson K.S. Schreck K.M. Hillmyer M.A. Toughening polylactide Polym. Rev. 2008 48 85 108 10.1080/15583720701834216
Baiardo M. Frisoni G. Scandola M. Rimelen M. Lips D. Ruffieux K. Wintermantel E. Thermal and mechanical properties of plasticized poly(l-lactic acid) J. Appl. Polym. Sci. 2003 90 1731 1738 10.1002/app.12549
Li D. Jiang Y. Lv S. Liu X. Gu J. Chen Q. Zhang Y. Preparation of plasticized poly (lactic acid) and its influence on the properties of composite materials PLoS ONE 2018 13 e0193520 29494654 10.1371/journal.pone.0193520
Ljungberg N. Wesslén B. Tributyl citrate oligomers as plasticizers for poly (lactic acid): Thermo-mechanical film properties and aging Polymer 2003 44 7679 7688 10.1016/j.polymer.2003.09.055
Maiza M. Benaniba M.T. Massardier-Nageotte V. Plasticizing effects of citrate esters on properties of poly(lactic acid) J. Polym. Eng. 2016 36 371 380 10.1515/polyeng-2015-0140
Martino V.P. Jiménez A. Ruseckaite R.A. Processing and characterization of poly(lactic acid) films plasticized with commercial adipates J. Appl. Polym. Sci. 2009 112 2010 2018 10.1002/app.29784
Ruellan A. Ducruet V. Domenek S. Chapter 5 Plasticization of poly(lactide) Poly(lactic acid) Science and Technology: Processing, Properties, Additives and Applications Jiménez A. Peltzer M. Ruseckaite R. The Royal Society of Chemistry Cambridge, UK 2015 124 170
Kfoury G. Raquez J.-M. Hassouna F. Odent J. Toniazzo V. Ruch D. Dubois P. Recent advances in high performance poly(lactide): From “green” plasticization to super-tough materials via (reactive) compounding Front. Chem. 2013 1 32 10.3389/fchem.2013.00032
Jacobsen S. Fritz H.G. Plasticizing polylactide—the effect of different plasticizers on the mechanical properties Polym. Eng. Sci. 1999 39 1303 1310 10.1002/pen.11517
Murariu M. Da Silva Ferreira A. Alexandre M. Dubois P. Polylactide (PLA) designed with desired end-use properties: 1. PLA compositions with low molecular weight ester-like plasticizers and related performances Polym. Adv. Technol. 2008 19 636 646 10.1002/pat.1131
Abbott S. Chemical compatibility of poly(lactic acid): A practical framework using Hansen solubility parameters Poly(lactic acid) Auras R. Lim L.-T. Selke S.E.M. Tsuji H. John Wiley & Sons, Inc. Hoboken, NJ, USA 2010 83 95
Detyothin S. Kathuria A. Jaruwattanayon W. Selke S.E.M. Auras R. Poly(lactic acid) blends Poly(lactic acid) Auras R. Lim L.-T. Selke S.E.M. Tsuji H. John Wiley & Sons, Inc. Hoboken, NJ, USA 2010 227 271
Athanasoulia I.-G. Tarantili P.A. Preparation and characterization of polyethylene glycol/poly(l-lactic acid) blends Pure Appl. Chem. 2017 89 141 152 10.1515/pac-2016-0919
Avolio R. Castaldo R. Avella M. Cocca M. Gentile G. Fiori S. Errico M.E. PLA-based plasticized nanocomposites: Effect of polymer/plasticizer/filler interactions on the time evolution of properties Compos. Part B Eng. 2018 152 267 274 10.1016/j.compositesb.2018.07.011
Jia P. Xia H. Tang K. Zhou Y. Plasticizers derived from biomass resources: A short review Polymers 2018 10 1303 10.3390/polym10121303 30961228
Shirai M.A. Müller C.M.O. Grossmann M.V.E. Yamashita F. Adipate and citrate esters as plasticizers for poly(lactic acid)/thermoplastic starch sheets J. Polym. Environ. 2015 23 54 61 10.1007/s10924-014-0680-9
Greco A. Ferrari F. Thermal behavior of PLA plasticized by commercial and cardanol-derived plasticizers and the effect on the mechanical properties J. Therm. Anal. Calorim. 2021 146 131 141 10.1007/s10973-020-10403-9
Kulinski Z. Piorkowska E. Gadzinowska K. Stasiak M. Plasticization of poly(l-lactide) with poly(propylene glycol) Biomacromolecules 2006 7 2128 2135 10.1021/bm060089m
Chaos A. Sangroniz A. Gonzalez A. Iriarte M. Sarasua J.-R. del Río J. Etxeberria A. Tributyl citrate as an effective plasticizer for biodegradable polymers: Effect of plasticizer on free volume and transport and mechanical properties Polym. Int. 2019 68 125 133 10.1002/pi.5705
Shi N. Dou Q. Crystallization behavior, morphology, and mechanical properties of poly(lactic acid)/tributyl citrate/treated calcium carbonate composites Polym. Compos. 2014 35 1570 1582 10.1002/pc.22810
Lemmouchi Y. Murariu M. Santos A.M.D. Amass A.J. Schacht E. Dubois P. Plasticization of poly(lactide) with blends of tributyl citrate and low molecular weight poly(d,l-lactide)-b-poly(ethylene glycol) copolymers Eur. Polym. J. 2009 45 2839 2848 10.1016/j.eurpolymj.2009.07.006
Yang Z. Bi H. Bi Y. Rodrigue D. Xu M. Feng X. Comparison between polyethylene glycol and tributyl citrate to modify the properties of wood fiber/polylactic acid biocomposites Polym. Compos. 2019 40 1384 1394 10.1002/pc.24872
Menčík P. Přikryl R. Stehnová I. Melčová V. Kontárová S. Figalla S. Alexy P. Bočkaj J. Effect of selected commercial plasticizers on mechanical, thermal, and morphological properties of poly(3-hydroxybutyrate)/Poly(lactic acid)/plasticizer biodegradable blends for three-dimensional (3D) print Materials 2018 11 1893 10.3390/ma11101893 30282917
Mekonnen T. Mussone P. Khalil H. Bressler D. Progress in bio-based plastics and plasticizing modifications J. Mater. Chem. A 2013 1 13379 13398 10.1039/c3ta12555f
Hassouna F. Raquez J.-M. Addiego F. Toniazzo V. Dubois P. Ruch D. New development on plasticized poly(lactide): Chemical grafting of citrate on PLA by reactive extrusion Eur. Polym. J. 2012 48 404 415 10.1016/j.eurpolymj.2011.12.001
Aliotta L. Vannozzi A. Panariello L. Gigante V. Coltelli M.-B. Lazzeri A. Sustainable micro and nano additives for controlling the migration of a biobased plasticizer from PLA-based flexible films Polymers 2020 12 1366 10.3390/polym12061366 32560520
Murariu M. Paint Y. Murariu O. Raquez J.-M. Bonnaud L. Dubois P. Current progress in the production of PLA–ZnO nanocomposites: Beneficial effects of chain extender addition on key properties J. Appl. Polym. Sci. 2015 48 132 10.1002/app.42480
Rasselet D. Caro-Bretelle A.-S. Taguet A. Lopez-Cuesta J.-M. Reactive compatibilization of PLA/PA11 blends and their application in additive manufacturing Materials 2019 12 485 10.3390/ma12030485
Standau T. Nofar M. Dörr D. Ruckdäschel H. Altstädt V. A review on multifunctional epoxy-based Joncryl® ADR chain extended thermoplastics Polym. Rev. 2022 62 296 350 10.1080/15583724.2021.1918710
Walha F. Lamnawar K. Maazouz A. Jaziri M. Rheological, morphological and mechanical studies of sustainably sourced polymer blends based on poly(lactic acid) and polyamide 11 Polymers 2016 8 61 10.3390/polym8030061
Al-Itry R. Lamnawar K. Maazouz A. Improvement of thermal stability, rheological and mechanical properties of PLA, PBAT and their blends by reactive extrusion with functionalized epoxy Polym. Degrad. Stab. 2012 97 1898 1914 10.1016/j.polymdegradstab.2012.06.028
Corre Y.-M. Duchet J. Reignier J. Maazouz A. Melt strengthening of poly (lactic acid) through reactive extrusion with epoxy-functionalized chains Rheol. Acta 2011 50 613 629 10.1007/s00397-011-0538-1
Villalobos M. Awojulu A. Greeley T. Turco G. Deeter G. Oligomeric chain extenders for economic reprocessing and recycling of condensation plastics Energy 2006 31 3227 3234 10.1016/j.energy.2006.03.026
Bocqué M. Voirin C. Lapinte V. Caillol S. Robin J.-J. Petro-based and bio-based plasticizers: Chemical structures to plasticizing properties J. Polym. Sci. Part A Polym. Chem. 2016 54 11 33 10.1002/pola.27917
Xiao H. Lu W. Yeh J.-T. Effect of plasticizer on the crystallization behavior of poly(lactic acid) J. Appl. Polym. Sci. 2009 113 112 121 10.1002/app.29955
Tábi T. Ageyeva T. Kovács J.G. Improving the ductility and heat deflection temperature of injection molded Poly(lactic acid) products: A comprehensive review Polym. Test. 2021 101 107282 10.1016/j.polymertesting.2021.107282
Varol N. Delpouve N. Araujo S. Domenek S. Guinault A. Golovchak R. Ingram A. Delbreilh L. Dargent E. Amorphous rigidification and cooperativity drop in semi−crystalline plasticized polylactide Polymer 2020 194 122373 10.1016/j.polymer.2020.122373
Wang R. Wan C. Wang S. Zhang Y. Morphology, mechanical properties, and durability of poly(lactic acid) plasticized with di(isononyl) cyclohexane-1,2-dicarboxylate Polym. Eng. Sci. 2009 49 2414 10.1002/pen.21490
Safandowska M. Rozanski A. Galeski A. Plasticization of polylactide after solidification: An effectiveness and utilization for correct interpretation of thermal properties Polymers 2020 12 561 10.3390/polym12030561
Wypych G. 10—Effect of plasticizers on properties of plasticized materials Handbook of Plasticizers 3rd ed. Wypych G. ChemTec Publishing Scarborough, ON, Canada 2017 209 332
Aliotta L. Cinelli P. Coltelli M.B. Lazzeri A. Rigid filler toughening in PLA-calcium carbonate composites: Effect of particle surface treatment and matrix plasticization Eur. Polym. J. 2019 113 78 88 10.1016/j.eurpolymj.2018.12.042
Spear M.J. Eder A. Carus M. 10—Wood polymer composites Wood Composites Ansell M.P. Woodhead Publishing Cambridge, UK 2015 195 249
Mousavi Z. Heuzey M.-C. Randall J. Carreau P.J. Enhanced properties of polylactide/polyamide 11 blends by reactive compatibilization Can. J. Chem. Eng. 2022 100 2475 2490 10.1002/cjce.24414
Han J. Zhang M. Zhang H. Liu H. Xu S. Effects of modified tributyl citrate as a novel environmentally friendly plasticizer on the mechanical property and migration stability of soft polyvinyl chloride J. Vinyl Addit. Technol. 2022 28 751 761 10.1002/vnl.21914
Jaszkiewicz A. Bledzki A.K. van der Meer R. Franciszczak P. Meljon A. How does a chain-extended polylactide behave?: A comprehensive analysis of the material, structural and mechanical properties Polym. Bull. 2014 71 1675 1690 10.1007/s00289-014-1148-8
