Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

Abstract The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm2. The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.

[1]  A. Müller,et al.  Surface-Grafted Hyperbranched Polymers via Self-Condensing Atom Transfer Radical Polymerization from Silicon Surfaces , 2001 .

[2]  R. Advíncula,et al.  Living Anionic Surface-Initiated Polymerization (LASIP) of a Polymer on Silica Nanoparticles , 2002 .

[3]  R. Schmidt,et al.  Photoinitiated polymerization of styrene from self-assembled monolayers on gold , 2002 .

[4]  Bin Yu,et al.  Controlled radical polymerization catalyzed by copper(I)–sparteine complexes , 1999 .

[5]  Didier Benoit,et al.  Controlled Synthesis of Polymer Brushes by “Living” Free Radical Polymerization Techniques , 1999 .

[6]  N. Ayres,et al.  Living Radical Polymerization Immobilized on Wang Resins: Synthesis and Harvest of Narrow Polydispersity Poly(methacrylate)s , 2001 .

[7]  A. Ulman,et al.  Nanocomposites by Surface-Initiated Living Cationic Polymerization of 2-Oxazolines on Functionalized Gold Nanoparticles , 2001 .

[8]  A. Curtis,et al.  Dextran and albumin derivatised iron oxide nanoparticles: influence on fibroblasts in vitro. , 2003, Biomaterials.

[9]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[10]  Z John Zhang,et al.  Atom transfer radical polymerization synthesis and magnetic characterization of MnFe2O4/polystyrene core/shell nanoparticles. , 2002, Journal of the American Chemical Society.

[11]  Shinpei Yamamoto,et al.  Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by the Combined Use of the Langmuir−Blodgett and Atom Transfer Radical Polymerization Techniques , 1998 .

[12]  Krzysztof Matyjaszewski,et al.  Handbook of radical polymerization , 2002 .

[13]  J. Rühe,et al.  Synthesis of Poly(styrene) Monolayers Attached to High Surface Area Silica Gels through Self-Assembled Monolayers of Azo Initiators , 1998 .

[14]  P. Todd,et al.  Field-assisted extraction of cells, particles and macromolecules. , 2002, Trends in biotechnology.

[15]  G. Baker,et al.  Surface-initiated atom transfer radical polymerization on gold at ambient temperature , 2000 .

[16]  S. Odenbach Ferrofluids—magnetically controlled suspensions , 2003 .

[17]  T. Patten,et al.  Preparation of Structurally Well-Defined Polymer−Nanoparticle Hybrids with Controlled/Living Radical Polymerizations , 1999 .

[18]  A. Kondo,et al.  Preparation of thermo-sensitive magnetic microspheres and their application to bioprocesses , 1999 .

[19]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[20]  I. Choi,et al.  Surface-Initiated Polymerization of l-Lactide: Coating of Solid Substrates with a Biodegradable Polymer , 2001 .

[21]  T. Fukuda,et al.  Atomic force microscopic study of stretching a single polymer chain in a polymer brush , 2000 .

[22]  Earl J. Bergey,et al.  Nanochemistry: Synthesis and Characterization of Multifunctional Nanoclinics for Biological Applications , 2002 .

[23]  H. Hamann,et al.  Polymer mediated self-assembly of magnetic nanoparticles. , 2002, Journal of the American Chemical Society.

[24]  Jennifer J. Jackiw,et al.  Ring-Opening Metathesis Polymerization from Surfaces , 1999 .

[25]  N. Abbott,et al.  Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring‐opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes” , 2001 .

[26]  W. Brittain,et al.  Synthesis of Polystyrene-block-poly(methyl methacrylate) Brushes by Reverse Atom Transfer Radical Polymerization , 2000 .

[27]  D. Walt,et al.  Preparation of Polymer Coated Gold Nanoparticles by Surface-Confined Living Radical Polymerization at Ambient Temperature , 2002 .

[28]  A. Schouten,et al.  GRAFTING KINETICS OF POLY(METHYL METHACRYLATE) ON MICROPARTICULATE SILICA , 1990 .

[29]  H. Otsuka,et al.  Polystyrene-Grafted Magnetite Nanoparticles Prepared through Surface-Initiated Nitroxyl-Mediated Radical Polymerization , 2003 .

[30]  Krzysztof Matyjaszewski,et al.  Polymers at interfaces : Using atom transfer radical polymerization in the controlled growth of homopolymers and block copolymers from silicon surfaces in the absence of untethered sacrificial initiator , 1999 .

[31]  K. Koh,et al.  Synthesis of Gold Nanoparticles Coated with Well-Defined, High-Density Polymer Brushes by Surface-Initiated Living Radical Polymerization , 2002 .

[32]  H. Kawaguchi,et al.  Hairy particles prepared by living radical graft-polymerization , 2002 .

[33]  B. Sumerlin,et al.  Facile preparation of transition metal nanoparticles stabilized by well-defined (co)polymers synthesized via aqueous reversible addition-fragmentation chain transfer polymerization. , 2002, Journal of the American Chemical Society.

[34]  A. Chilkoti,et al.  Surface-Initiated Free Radical Polymerization of Polystyrene Micropatterns on a Self-Assembled Monolayer on Gold , 2001 .