Comparison of surface confined ATRP and SET‐LRP syntheses for a series of amino (meth)acrylate polymer brushes on silicon substrates

A series of poly(amino (meth)acrylate) brushes, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA), poly(2-(dimethylamino)ethyl acrylate) (PDMAEA), poly(2-(tert-butylamino)ethyl methacrylate) (PTBAEMA), has been synthesized via surface-confined controlled/living radical polymerizations using surface-confined initiator from silane self-assembled monolayers (SAMs) on silicon (Si) wafer substrates. Chemical methods and efficacies for two types of living radical polymerization, atom transfer radical (ATRP) and single electron transfer (SET-LRP), are described and contrasted for the surface confined polymerization of poly(amino (meth)acrylate)s. Effects of solvent, catalyst/ligand system, and temperature on polymerization success were examined. Chemical compositions after each reaction step were characterized with FTIR spectroscopy, contact angle goniometry, and X-ray photoelectron spectroscopy while the SAM and polymer brush thicknesses were measured with spectroscopic ellipsometry. For the first time, this study demonstrates successful surface-confined polymerization of a series of poly(amine (meth)acrylate) brushes from Si-SAM substrates using a copper metal electron donor catalyst.

[1]  W. Brittain,et al.  Synthesis, Characterization, and Properties of Polyelectrolyte Block Copolymer Brushes Prepared by Atom Transfer Radical Polymerization and Their Use in the Synthesis of Metal Nanoparticles , 2003 .

[2]  P. Topham,et al.  Controlled growth of poly(2-(diethylamino)ethyl methacrylate) brushes via atom transfer radical polymerisation on planar silicon surfaces , 2006 .

[3]  S. M. Kilbey,et al.  Effect of Catalyst Deactivation on Polymerization of Electrolytes by Surface-Confined Atom Transfer Radical Polymerization in Aqueous Solutions , 2006 .

[4]  W. Brittain,et al.  Synthesis, characterization, and properties of tethered polystyrene-b-polyacrylate brushes on flat silicate substrates , 2000 .

[5]  K. Matyjaszewski,et al.  ATRP synthesis of amphiphilic random, gradient, and block copolymers of 2-(dimethylamino)ethyl methacrylate and n-butyl methacrylate in aqueous media. , 2003, Biomacromolecules.

[6]  K. Neoh,et al.  Surface-initiated atom transfer radical polymerization from halogen-terminated Si(111) (Si-X, X = Cl, Br) surfaces for the preparation of well-defined polymer-Si hybrids. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[7]  M. Galleni,et al.  Polyolefin matrixes with permanent antibacterial activity: preparation, antibacterial activity, and action mode of the active species. , 2006, Biomacromolecules.

[8]  K. Matyjaszewski,et al.  High capacity, charge-selective protein uptake by polyelectrolyte brushes. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[9]  V. Percec,et al.  Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 °C , 2009 .

[10]  S. Armes,et al.  Synthesis of Shell Cross-Linked Micelles at High Solids in Aqueous Media , 2000 .

[11]  A. Rossi,et al.  Synthesis of poly(methacrylic acid) brushes via surface-initiated atom transfer radical polymerization of sodium methacrylate and their use as substrates for the mineralization of calcium carbonate , 2007 .

[12]  Ian D. Rees,et al.  Using Atom Transfer Radical Polymerization To Amplify Monolayers of Initiators Patterned by Microcontact Printing into Polymer Brushes for Pattern Transfer , 2000 .

[13]  Y. Gan,et al.  Controlled polymerizations of 2-(dialkylamino)ethyl methacrylates and their block copolymers in protic solvents at ambient temperature via ATRP , 2004 .

[14]  S. Armes,et al.  DIRECT SYNTHESIS OF CONTROLLED-STRUCTURE PRIMARY AMINE-BASED METHACRYLIC POLYMERS BY LIVING RADICAL POLYMERIZATION , 2007 .

[15]  G. Mantovani,et al.  Copper mediated living radical polymerisation: interactions between monomer and catalystBased on the presentation given at Dalton Discussion No. 6, 9?11th September 2003, University of York, UK. , 2003 .

[16]  S. Armes,et al.  Surface polymerization from planar surfaces by atom transfer radical polymerization using polyelectrolytic macroinitiators , 2007 .

[17]  M. Galleni,et al.  Synthesis of copolymer brushes endowed with adhesion to stainless steel surfaces and antibacterial properties by controlled nitroxide-mediated radical polymerization. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[18]  K. Matyjaszewski,et al.  Synthesis and in situ atomic force microscopy characterization of temperature-responsive hydrogels based on poly(2-(dimethylamino)ethyl methacrylate) prepared by atom transfer radical polymerization. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[19]  Darren M. Jones,et al.  Controlled growth of triblock polyelectrolyte brushes. , 2002, Chemical communications.

[20]  D. Hirt,et al.  Surface Characterization of Linear Low-Density Polyethylene Films Modified with Fluorinated Additives , 2003 .

[21]  N. Markova,et al.  Combination of electrografting and atom-transfer radical polymerization for making the stainless steel surface antibacterial and protein antiadhesive. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[22]  K. Matyjaszewski,et al.  Role of Cu0 in Controlled/“Living” Radical Polymerization , 2007 .

[23]  R. Koepsel,et al.  Permanent, nonleaching antibacterial surfaces. 1. Synthesis by atom transfer radical polymerization. , 2004, Biomacromolecules.

[24]  Michael J. Fasolka,et al.  Effect of Block Length on Solvent Response of Block Copolymer Brushes: Combinatorial Study with Block Copolymer Brush Gradients , 2006 .

[25]  N. Ayres,et al.  A Facile Route to Poly(acrylic Acid) Brushes Using Atom Transfer Radical Polymerization , 2006 .

[26]  K. Matyjaszewski,et al.  Synthesis of Well-Defined Amphiphilic Block Copolymers with 2-(Dimethylamino)ethyl Methacrylate by Controlled Radical Polymerization , 1999 .

[27]  Shiping Zhu,et al.  Synthesis and Characterization of Comb-Branched Polyelectrolytes. 1. Preparation of Cationic Macromonomer of 2-(Dimethylamino)ethyl Methacrylate by Atom Transfer Radical Polymerization , 2000 .

[28]  Shiping Zhu,et al.  Atom transfer radical polymerization of 2‐(dimethylamino)ethyl methacrylate in aqueous media , 2000 .

[29]  K. Neoh,et al.  Modification of Titanium via Surface-Initiated Atom Transfer Radical Polymerization (ATRP) , 2006 .

[30]  N. Pantoustier,et al.  Synthesis and swelling behavior of pH-responsive polybase brushes. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[31]  R. Koepsel,et al.  Antibacterial polypropylene via surface-initiated atom transfer radical polymerization. , 2007, Biomacromolecules.

[32]  K. Matyjaszewski,et al.  Optimization of atom transfer radical polymerization using Cu(I)/ tris(2-(dimethylamino)ethyl)amine as a catalyst , 2000 .

[33]  K. Matyjaszewski,et al.  Water-Dispersible Carbon Black Nanocomposites Prepared by Surface-Initiated Atom Transfer Radical Polymerization in Protic Media , 2006 .

[34]  Li Liu,et al.  Double-responsive polymer brushes on the surface of colloid particles. , 2006, Journal of colloid and interface science.

[35]  Feng Zhou,et al.  Probing the responsive behavior of polyelectrolyte brushes using electrochemical impedance spectroscopy. , 2007, Analytical chemistry.

[36]  S. Martin,et al.  Responsive brushes and gels as components of soft nanotechnology. , 2005, Faraday discussions.

[37]  D. Haddleton,et al.  Effect of DMSO used as solvent in copper mediated living radical polymerization , 2004 .

[38]  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 .

[39]  V. Percec,et al.  Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C. , 2006, Journal of the American Chemical Society.

[40]  B. Tighe,et al.  Responsive hydrophobically associating polymers: a review of structure and properties. , 2001, Advanced drug delivery reviews.

[41]  M. Cunningham,et al.  Surface-initiated nitroxide-mediated radical polymerization of 2-(dimethylamino)ethyl acrylate on polymeric microspheres , 2006 .

[42]  K. Neoh,et al.  Polymer Microspheres with Permanent Antibacterial Surface from Surface-Initiated Atom Transfer Radical Polymerization , 2005 .

[43]  Guodong Zheng,et al.  Grafting of Poly(alkyl (meth)acrylates) from Swellable Poly(DVB80-co-HEMA) Microspheres by Atom Transfer Radical Polymerization , 2002 .

[44]  S. Armes,et al.  Synthesis and aqueous solution properties of polyelectrolyte-grafted silica particles prepared by surface-initiated atom transfer radical polymerization. , 2003, Journal of colloid and interface science.

[45]  N. Ayres,et al.  Stimuli-responsive polyelectrolyte polymer brushes prepared via atom-transfer radical polymerization. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[46]  M. Ignatova,et al.  Design of antibacterial surfaces by a combination of electrochemistry and controlled radical polymerization. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[47]  Toru Maekawa,et al.  Magnetic carbon nanotubes: synthesis by electrostatic self-assembly approach and application in biomanipulations. , 2006, The journal of physical chemistry. B.

[48]  Shiping Zhu,et al.  Controlled Grafting of Well-Defined Polymers on Hydrogen-Terminated Silicon Substrates by Surface-Initiated Atom Transfer Radical Polymerization , 2003 .

[49]  Zhang,et al.  Controlled/"Living" Radical Polymerization of 2-(Dimethylamino)ethyl Methacrylate. , 1998, Macromolecules.

[50]  S. Armes,et al.  Unexpected Transesterification of Tertiary Amine Methacrylates during Methanolic ATRP at Ambient Temperature: A Cautionary Tale , 2002 .

[51]  K. Matyjaszewski,et al.  Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization. , 2008, Journal of the American Chemical Society.

[52]  H. Möhwald,et al.  Colloidally stable amphibious nanocrystals derived from poly{[2-(dimethylamino)ethyl] methacrylate} capping. , 2005, Angewandte Chemie.