Study on the preparation and characterization of biodegradable polylactide/multi-walled carbon nanotubes nanocomposites

In this study, polylactide/multi-walled carbon nanotubes (PLA/MWNTs) hybrids were prepared by means of a melt blending method. To enhance the compatibility between PLA and MWNTs, the acrylic acid grafted polylactide (PLA-g-AA) and the multihydroxyl-functionalized MWNTs (MWNTseOH) were used to replace PLA and MWNTs, respectively. The crude MWNTs were chemically oxidized by a mixture of H2SO4 and HNO3 and then reacted with thionyl chloride to functionalize them with chlorocarbonyl groups (MWNTseCOCl). The MWNTseOH was finally obtained by the reaction of MWNTseCOCl and 1,6-hexanediol. The resulting products have been characterized by FTIR, 13 C solid-state NMR, TGA, DMA, SEM, TEM, and Instron mechanical tester. Due to the formation of ester groups through the reaction between carboxylic acid groups of PLA-g-AA and hydroxyl groups of MWNTseOH, results demonstrated dramatic enhancement in thermal and mechanical properties of PLA, for example, 77 � C increase in initial decomposition temperature with the addition of only 1 wt%. Based on the result of thermal and mechanical examinations, it was found that the optimal amount of MWNTseOH was 1 wt% because excess MWNTseOH caused separation of the organic and inorganic phases and lowered their compatibility. 2007 Elsevier Ltd. All rights reserved.

[1]  L. Avérous,et al.  Poly(lactic acid): plasticization and properties of biodegradable multiphase systems , 2001 .

[2]  K. Br,et al.  Current status of DNA vaccines in veterinary medicine. , 2000 .

[3]  Richard A. Vaia,et al.  Synthesis and properties of two-dimensional nanostructures by direct intercalation of polymer melts in layered silicates , 1993 .

[4]  Hsu-Chiang Kuan,et al.  Molecular mobility of free‐radical‐functionalized carbon‐nanotube/siloxane/poly(urea urethane) nanocomposites , 2005 .

[5]  Philippe Dubois,et al.  Polyester layered silicate nanohybrids by controlled grafting polymerization , 2002 .

[6]  D. Yan,et al.  Poly(ϵ‐caprolactone)‐Functionalized Carbon Nanotubes and Their Biodegradation Properties , 2006 .

[7]  Ya‐Ping Sun,et al.  Polymeric Carbon Nanocomposites from Carbon Nanotubes Functionalized with Matrix Polymer , 2003 .

[8]  Minna Hakkarainen,et al.  Aliphatic polyesters : Abiotic and biotic degradation and degradation products , 2002 .

[9]  Y. Ikada,et al.  Blends of aliphatic polyesters. II. Hydrolysis of solution‐cast blends from poly(L‐lactide) and poly(E‐caprolactone) in phosphate‐buffered solution , 1998 .

[10]  Quan Qing,et al.  Effect of Chemical Oxidation on the Structure of Single-Walled Carbon Nanotubes , 2003 .

[11]  Otto Zhou,et al.  Fabrication and Properties of Composites of Poly(ethylene oxide) and Functionalized Carbon Nanotubes , 2002 .

[12]  Robert H. Hauge,et al.  Poly(vinyl alcohol)/SWNT Composite Film , 2003 .

[13]  Eklund,et al.  Solution properties of single-walled carbon nanotubes , 1998, Science.

[14]  Hung-Chieh Tsai,et al.  Preparing a Styrenic Polymer Composite Containing Well-Dispersed Carbon Nanotubes: Anionic Polymerization of a Nanotube-Bound p-Methylstyrene , 2004 .

[15]  J. Lunt Large-scale production, properties and commercial applications of polylactic acid polymers , 1998 .

[16]  Allan S Hoffman,et al.  Hydrogels for biomedical applications. , 2002, Advanced drug delivery reviews.

[17]  T. Kissel,et al.  Branched biodegradable polyesters for parenteral drug delivery systems. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

[18]  Daniel E. Resasco,et al.  Functionalization of Single-Walled Carbon Nanotubes with Polystyrene via Grafting to and Grafting from Methods , 2004 .

[19]  K. Besteman,et al.  Enzyme-Coated Carbon Nanotubes as Single-Molecule Biosensors , 2003 .

[20]  H. Wagner,et al.  Mechanical Properties of Functionalized Single‐Walled Carbon‐Nanotube/Poly(vinyl alcohol) Nanocomposites , 2005 .

[21]  J. L. Willett,et al.  Biodegradation of starch/polylactic acid/poly(hydroxyester-ether) composite bars in soil , 2003 .

[22]  Hui Hu,et al.  Chemically Functionalized Carbon Nanotubes as Substrates for Neuronal Growth. , 2004, Nano letters.

[23]  Jun Li,et al.  Poly-l-lysine Functionalization of Single-Walled Carbon Nanotubes , 2004 .

[24]  S. Shinkai,et al.  Self-Organization of PEO-graft-Single-Walled Carbon Nanotubes in Solutions and Langmuir−Blodgett Films , 2001 .

[25]  John E. Anthony,et al.  Thermogravimetric Analysis of the Oxidation of Multiwalled Carbon Nanotubes: Evidence for the Role of Defect Sites in Carbon Nanotube Chemistry , 2002 .

[26]  Jeffrey A Hubbell,et al.  Photopolymerized hyaluronic acid-based hydrogels and interpenetrating networks. , 2003, Biomaterials.

[27]  Elazer R. Edelman,et al.  Adv. Drug Delivery Rev. , 1997 .

[28]  Frank T. Fisher,et al.  Effects of nanotube waviness on the modulus of nanotube-reinforced polymers , 2002 .

[29]  P. Watts,et al.  Growing Multihydroxyl Hyperbranched Polymers on the Surfaces of Carbon Nanotubes by in Situ Ring-Opening Polymerization , 2004 .

[30]  I-Chun Liu,et al.  Preparing a polystyrene-functionalized multiple-walled carbon nanotubes via covalently linking acyl chloride functionalities with living polystyryllithium , 2004 .

[31]  T. Kashiwagi,et al.  Thermal Degradation and Flammability Properties of Poly(propylene)/Carbon Nanotube Composites , 2002 .

[32]  P. Gruber,et al.  Polylactic Acid Technology , 2000 .

[33]  T. Kotaka,et al.  Dispersed structure and ionic conductivity of smectic clay/polymer nanocomposites , 2001 .

[34]  G. Botton,et al.  Polymerization from the surface of single-walled carbon nanotubes - preparation and characterization of nanocomposites. , 2003, Journal of the American Chemical Society.

[35]  Karen Lozano,et al.  Reinforcing Epoxy Polymer Composites Through Covalent Integration of Functionalized Nanotubes , 2004 .

[36]  Werner J. Blau,et al.  High Performance Nanotube‐Reinforced Plastics: Understanding the Mechanism of Strength Increase , 2004 .

[37]  Chin-San Wu,et al.  In situ polymerization of silicic acid in polyethylene–octene elastomer: Properties and characterization of the hybrid nanocomposites , 2003 .

[38]  F. Chang,et al.  Preparation and crystallization behavior of syndiotactic polystyrene-clay nanocomposites , 2001 .

[39]  Chin-San Wu,et al.  A new biodegradable blends prepared from polylactide and hyaluronic acid , 2005 .

[40]  S. Girois,et al.  Polym. Degrad. Stab. , 1996 .

[41]  Shimou Chen,et al.  Preparation of Poly(acrylic acid) Grafted Multiwalled Carbon Nanotubes by a Two-Step Irradiation Technique , 2006 .

[42]  Jae Whan Cho,et al.  Polymeric nanocomposites of polyurethane block copolymers and functionalized multi-walled carbon nanotubes as crosslinkers , 2006 .

[43]  R. Ramasubramaniam,et al.  A Versatile, Molecular Engineering Approach to Simultaneously Enhanced, Multifunctional Carbon‐Nanotube– Polymer Composites , 2006 .

[44]  X. Sun,et al.  Physical properties of poly(lactic acid) and starch composites with various blending ratios , 2000 .