[en] Polylactide (PLA)/clay nanocomposites have been prepared by in situ ring-opening polymerization in supercritical carbon dioxide. Depending on the type of organoclay used, polylactide chains can be grafted onto the clay surface, leading to an exfoliated morphology. Nanocomposites with high clay contents (30–50 wt.%), called masterbatches, have also been successfully prepared and were recovered as fine powders thanks to the unique properties of the supercritical fluid. Dilution of these masterbatches into commercial l-polylactide by melt blending has led to essentially exfoliated nanocomposites containing 3 wt.% of clay. The mechanical properties of these materials have been assessed by flexion and impact tests. Significant improvements of stiffness and toughness have been observed for the PLA/clay nanocomposites compared to the pure matrix, together with improved impact resistance.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Urbanczyk, Laetitia ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Ngoundjo, Fred; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Alexandre, Michaël ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Calberg, Cédric ; Université de Liège - ULiège > Department of Applied Chemistry > Laboratory of Industrial Chemistry
Language :
English
Title :
Synthesis of polylactide/clay nanocomposites by in situ intercalative polymerization in supercritical carbon dioxide
The "Région Wallonne" in the frame of the "WINNOMAT" program "PROCOMO" BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
Ray S.S., Maiti P., Okamoto M., Yamada K., and Ueda K. New polylactide/layered silicate nanocomposites. 1. Preparation, characterization, and properties. Macromolecules 35 (2002) 3104-3110
Ray S.S., Okamoto K., Yamada K., and Okamoto M. Novel porous ceramic material via burning of polylactide/layered silicate nanocomposite. Nano Lett 2 (2002) 25-423
Wells S.L., and DeSimone J.M. CO2 technology platform: an important tool for environmental problem solving. Angew Chem Int Ed 40 (2001) 518-527
Stassin F., Halleux O., and Jérôme R. Ring-opening polymerization of ε-caprolactone in supercritical carbon dioxide. Macromolecules 34 (2001) 775-781
Bratton D., Brown M., and Howdle S.M. Suspension polymerization of l-lactide in supercritical carbon dioxide in the presence of a triblock copolymer stabilizer. Macromolecules 36 (2003) 5908-5911
Lepoittevin B., Pantoustier N., Alexandre M., Calberg C., Jérôme R., and Dubois P. Polyester layered silicate nanohybrids by controlled grafting polymerization. J Mater Chem 12 (2002) 3528-3532
Paul M.A., Alexandre M., Degée P., Calberg C., Jérôme R., and Dubois P. Exfoliated polylactide/clay nanocomposites by in situ coordination-insertion polymerization. Macromol Rapid Commun 24 9 (2003) 66-561
Paul M.A., Delcourt C., Alexandre M., Degée P., Monteverde F., Rulmont A., and Dubois P. (Plasticized) polylactide/(organo-)clay nanocomposites by in situ intercalative polymerization. Macromol Chem Phys 206 (2005) 484-498
Zerda A.S., Caskey T.C., and Lesser A.J. Highly concentrated intercalated silicate nanocomposites: synthesis and characterization. Macromolecules 36 (2003) 1603-1608
Zhao Q., and Samulski T. In situ polymerization of poly(methyl methacrylate)/clay nanocomposites in supercritical carbon dioxide. Macromolecules 38 (2005) 7967-7971
Yan C., Ma L., and Yang J. Preparation of polystyrene/montmorillonite nanocomposites in supercritical carbon dioxide. J Appl Polym Sci 98 (2005) 22-28
Li J., Xu Q., Peng Q., Pang M., He S., and Zhu C. Supercritical CO2 -assisted synthesis of polystyrene/clay nanocomposites via in situ intercalative polymerization. J Appl Polym Sci 100 (2006) 671-676
Zhao Q., and Samulski E.T. A comparative study of poly(methyl methacrylate) and polystyrene/clay nanocomposites prepared in supercritical carbon dioxide. Polymer 47 (2006) 663-671
Calberg C, Stassin F, Halleux O, Dubois P, Panoustier N, Alexandre M et al. Nanocomposite polyester preparation method. WO/2002/081541.
Urbanczyk L., Calberg C., Stassin F., Alexandre M., Jérôme R., Jérôme C., et al. Synthesis of PCL/clay masterbatches in supercritical carbon dioxide. Polymer 49 (2008) 3979-3986
Lepoittevin B., Panoustier N., Devalckenaere M., Alexandre M., Calberg C., Jérôme R., et al. Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt Intercalation: a masterbatch process. Polymer 44 (2003) 2033-2040
Kiersnowski A., and Piglowski J. Polymer-layered silicate nanocomposites based on poly(ε-caprolactone). Eur Polym J 40 (2004) 1199-1207
Urbanczyk L., Calberg C., Benali S., Bourbigot S., Espuche E., Gouanvé F., et al. Poly(caprolactone)/clay masterbatches prepared in supercritical CO2 as efficient clay delamination promoters in poly(styrene-co-acrylonitrile). J Mater Chem 18 (2008) 4623-4630
Kendall J.L., Canelas D.A., Young J.L., and DeSimone J.M. Polymerizations in supercritical carbon dioxide. Chem Rev 99 (1999) 543-563
Woods H.M., Silva M.M.C.G., Nouvel C., Shakesheff K.M., and Howdle S.M. Materials processing in supercritical carbon dioxide: surfactants, polymers and biomaterials. J Mater Chem 14 (2004) 1663-1678
Stassin F., and Jérôme R. Polymerization of (l,l)-lactide and copolymerization with ε-caprolactone initiated by dibutyltin dimethoxide in supercritical carbon dioxide. J Pol Sci A Pol Chem 43 (2005) 2777-2789
Homminga D., Goderis B., Hoffman S., Reynaers H., and Groeninckx G. Influence of shear flow on the preparation of polymer layered silicate nanocomposites. Polymer 46 (2005) 9941-9954
