Surface-initiated Atom Transfer Radical Polymerization and Solution Intercalation Methods for Preparation of Cellulose-G-PS-G-PAN/MMT Bionanocomposite

Document Type : Research Paper


1 Zanjan University

2 Faculty of Science, University of Zanjan, Zanjan, Iran

3 Payame Noor University


Cellulose was modified by polystyrene (PS) and polyacrylonitrile (PAN) via free radical and living radical polymerization, and then cellulose was used as the matrix in the preparation of polymer/clay nanocomposite, through a solution intercalation method. For this purpose, first, the graft polymerization of styrene (St) onto cellulose fibers was performed by using suspension polymerization and the free-radical polymerization technique in the presence of potassium persulfate (PPS). Second, the synthesized cellulose-graft-polystyrene was brominated by N-bromosuccinimide (NBS) to obtain polymers with bromine a group. Third, the brominated cellulose fibers were used as macroinitiators in the atom transfer radical polymerization (ATRP) of acrylonitrile (AN) in the presence of CuCl / 2, 2’-bipyridine (Bpy) catalyst system in THF solvent at 90˚C to prepare the cellulose-graft-polystyrene–graft–polyacrylonitrile. Forth, for preparing the modified clay, Na-MMT was mixed with hexadecyl trimethyl ammonium chloride salt. Finally, cellulose-graft-polystyrene–graft–polyacrylonitrile/organoclay bionanocomposite was prepared in CCl4 by a solution intercalation method. Then, the structure of the obtained terpolymer was investigated by FT-IR, DSC, TGA, XRD, and SEM techniques. Moreover, the structure of the bionanocomposite was probed by XRD, SEM, and TEM images.


Sinha Ray S. and Bousmina M., “Biodegradable Polymers and their Layered Silicate Nanocomposites: in Greening the 21st Century Materials World,” Progress in Material Science, 2005, 50, 962–1079.
Armentano I., Dottori M., Fortunati E., Mattioli S. et al., “Biodegradable Polymer Matrix Nanocomposites for Tissue Engineering: a Review,” Polymer Degradation and Stability, 2010, 95, 2126–2146.
Kotek J., Kubies D., Baldrian J., and Kovárová, J., “Biodegradable Polyester Nanocomposites: the Effect of Structure on Mechanical and Degradation Behavior,” Eur. Polym. J., 2011, 47, 2197–2207.
Leaversuch R., “Plastics Technology [online Magazine; biomaterials and materials zone],, Sept.3, 2002 [April 2013].
Fortunati E., Armentano I., Zhou Q., Iannoni A., et al., “Multifunctional Bionanocomposite Films of Poly(lactic acid), Cellulose Nanocrystals and Silver Nanoparticles,” Carbohydr. Polym., 2012, 87, 1596–1605.
Fortunati E., Armentano I., Zhou Q., Puglia D., et al., “Microstructure and Nonisothermal Cold Crystallization of PLA Composites Based on Silver Nanoparticles and Nanocrystalline Cellulose,” Polym. Degrad. Stabil., 2012, 97, 2027–2036.
Darder M., Aranda P., and Ruiz-Hitzky E., “Bionanocomposites: a New Concept of Ecological, Bioinspired, and Functional Hybrid Materials,” Adv. Mater., 2007, 19, 1309–1319.
Raka L., Bogoeva-Gaceva G., Lu K., and Loos J., “Characterization of Latex-based Isotactic Polypropylene/Clay Nanocomposites,” Polymer, 2009, 50, 3739–3746.
Jaymand, M., “Surface Modification of Montmorillonite with Novel Modifier and Preparation of Polystyrene/ Montmorillonite Nanocomposite by In Situ Radical Polymerization,” J. Polym. Res., 2011, 18, 957–963.
Klemm D., Heublein B., Fink H-P., and Bohn A., “Cellulose: Fascinating Biopolymer and Sustainable Raw Material,” Angew Chem. Int. Ed., 2005, 44, 3358-3393.
Simkovic I., “What Could Be Greener than Composites Made from Polysaccharides,” Carbohydr. Polym., 2008, 74, 759-762.
Bredereck K. and Hermanutz F., “Man- Made Cellulosics,” Rev. Prog. Color. Relat. Top., 2005, 35, 59-75.
Klemm D., Philipp B., Heinze T., Heinze U., et al., “Comprehensive Cellulose Chemistry,” Wiley-VCH, Germany, 1998.
Hebeish A. and Guthrie J. T., “The Chemistry and Technology of Cellulosic Copolymers,” Springer-Verlag, Berlin, 1981.
Khan F., “Photoinduced Graft-copolymer Synthesis and Characterization of Methacrylic Acid onto Natural Biodegradable Lignocellulose Fiber,” Biomacromolecules, 2004, 5, 1078–1088
Roy D., Semsarilar M., Guthrie J. T., and Perrier S., “Cellulose Modification by Polymer Grafting: a Review,” Chem. Soc. Rev., 2009, 38, 2046–2064.
Xia J., and Matyjaszewski K., “Controlled /“Living” Radical Polymerization Atom Transfer Radical Polymerization Using Multidentate Amine Ligands,” Macromolecules, 1997, 30, 7697-7700.
Koenig, H. S. and Roberts C. W., “Vinylbenzyl Ethers of Cellulose. Preparation and Polymerization,” J. Appl. Polym. Sci., 1974, 18, 651–666.
Abbasian M. and Esmaeily Shoja Bonab S., “Nitroxide Mediated and Atom Transfer Radical Graft Polymerization of Atactic Polymers onto Syndiotactic Polystyrene,” Braz. J. Chem. Eng., 2012, 29, 285-294.
Abbasian M., Esmaeily Shoja S., and Shahparian M., “Chemical Modification of Polypropylene by Nitroxide Mediated Living Radical Graft Polymerization of Styrene,” Iran. Polym. J., 2013, 22, 209-218.
Abbasian M. and Mahi R., “In Situ Synthesis of Polymer-silica Nanocomposites by Living Radical Polymerization Using TEMPO Initiator,” J. Exp. Nanosci., 2014, 9, 785-798.
Barner L., “Surface Grafting via the Reversible Addition Fragmentation Chain Transfer (RAFT) Process: from Polypropylene Beads to Core-shell Microspheres,” Aust. J. Chem., 2003, 56, 1091.
Perrier S., Takolpuckdee P., Westwood J., and Lewis D. M., “Versatile Chain Transfer Agents for Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization to Synthesize Functional Polymeric Architectures,” Macromolecules, 2004, 37, 2709–2717.
Takolpuckdee P., “Chain Transfer Agents for RAFT Polymerization: Molecules to Design Functionalized Polymers,” Aust. J. Chem., 2005, 58, 66–66.
Abbasian M., Esmaeily Shoja S., and Shahparian M., “Synthesis of PMMA-graft-MAH-graftPP/organoclay Nanocomposites via Metal Catalyzed Radical Polymerization and Solvent Blending Methods,” Polym. Plast. Technol. Eng., 2012, 51, 1589-159
Abbasian M., Fathi A., Entezami A. A., and Jaymand M., “Preparation and Characterization of Hyperbranched Polystyrene Nanocomposite Synthesized by Living Radical Polymerization and Solution Intercalation Method,” Iran. J. Polym. Sci. Technol., 2012, 24, 433- 443.
Abbasian M. and Khakpour Ali N, “Synthesis of Poly (methyl methacrylate)/Zinc Oxide Nanocomposite with Core-shell Morphology by Atom Transfer Radical Polymerization,” J. Macromol. Sci, Pure. Appl. Chem., 2013, 50, 966-975.
Summerlin B. S, Tsarevsky N. V., Louche G., Matyjaszewski K., et al., “Highly Efficient “Click” Functionalization of Poly (3- Azidopropylmethacrylate) Prepared by ATRP,” Macromolecules, 2005, 38, 7540-7545.
Sinha Ray S. and Okamoto M., “Polymer/Layered Silicate Nanocomposites: a Review from Preparation to Processing,” Prog. Polym. Sci., 2003, 28, 1539–1641.
Jiang G., Huang H. X., and Chen Z. K., “Microstructure and Thermal Behavior of Polylactide / Clay Nanocomposites Melt Compounded under Supercritical CO2Adv. Polym. Tech., 2011, 30, 174-182.
Urbanczyk L., Ngoundjo F., Alexandre M., Jerome C., et al., “Synthesis of Polylactide/Clay Nanocomposites by In Situ Intercalative Polymerization in Supercritical Carbon Dioxide,” Eur. Polym. J., 2009, 45, 643–648.
Moad G. and Solomon D. H., “The Chemistry of Radical Polymerization,” Elsevier Ltd, Oxford, 2006.
Ibrahim M. D., Mondal H., Uraki Y., Ubukata M. et al., “Graft Polymerization of Vinyl Monomers onto Cotton Fibers Pretreated with Amines,” Cellulose, 2008, 15, 581–592.
Lin C. X., Zhan H. U., Liu M. H., Fu S. U., et al., “Rapid Homogeneous Preparation of Cellulose Graft Copolymer in BMIMCL under Microwave Irradiation,” J. Appl. Polym. Sci., 2010, 118, 399-404.
Toledano-Thompson T., Loria- Bastarrachea M. I., and Aguilar-Vega M. J., “Characterization of Henequen Cellulose Microfibers Treated with an Epoxide and Grafted with Poly(acrylic acid),” Carbohyd. Polym., 2005, 62, 67–73.
Ghosh P. and Das D., “Modification of Cotton by Acrylic Acid (AA) in the Presence of NaH2PO4 and K2S2O8 as Catalysts under Thermal Treatment,” Eur. Polym. J., 2000, 36, 2505-2511.
De Oliveira R. L., Da Silva Barud H., D Assuncao R. M. N., Da Silva Meireles C. et al., “Synthesis and Characterization of Microcrystalline Cellulose Produced from Bacterial Cellulose,” J. Therm. Anal. Calorim., 2011, 106, 703–709.
El-Khouly A.S., Takahashi Y., Takada A., Safaan A. A. et al., “Characterization and Thermal Stability of Cellulose-graft- Polyacrylonitrile Prepared by Using KMnO4/Citric Acid Redox System,” J. Appl. Polym. Sci., 2010, 116, 1788-1795.