Controlled/living radical polymerization: Features, developments, and perspectives

Abstract Recent mechanistic developments in the field of controlled/living radical polymerization (CRP) are reviewed. Particular emphasis is placed on structure–reactivity correlations and “rules” for catalyst selection in atom transfer radical polymerization (ATRP), for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerization (SFRP), including organic and transition metal persistent radicals. Novel methods of fine tuning initiation, activation, and deactivation processes for all techniques are discussed, including activators regenerated by electron transfer (ARGET) and initiators for continuous activator regeneration (ICAR) ATRP, whereby Cu catalyst concentrations in ATRP can be lowered to just 10 ppm. Progress made in each technique related to the synthesis of both high and low molecular weight polymers, end functional polymers, block copolymers, expanding the range of polymerizable monomers, synthesis of hybrid materials, environmental issues, and polymerization in aqueous media is thoroughly discussed and compared.

[1]  K. Matyjaszewski,et al.  Simultaneous Reverse and Normal Initiation in Atom Transfer Radical Polymerization , 2001 .

[2]  K. Matyjaszewski,et al.  Utilizing Halide Exchange To Improve Control of Atom Transfer Radical Polymerization , 1998 .

[3]  Zhiqun Lin,et al.  One-Step Formation of Functionalized Block Copolymers , 2000 .

[4]  K. Matyjaszewski,et al.  Synthesis and characterization of graft copolymers of poly(vinyl chloride) with styrene and (meth)acrylates by atom transfer radical polymerization , 1998 .

[5]  K. Matyjaszewski,et al.  Extended X‐ray Absorption Fine Structure Study of Copper(I) and Copper(II) Complexes in Atom Transfer Radical Polymerization , 2003 .

[6]  K. Matyjaszewski,et al.  Tridentate Nitrogen-Based Ligands in Cu-Based ATRP: A Structure−Activity Study , 2001 .

[7]  K. Bernaerts,et al.  Design of novel poly(methyl vinyl ether) containing AB and ABC block copolymers by the dual initiator strategy , 2005 .

[8]  K. Matyjaszewski,et al.  Morphology and thermomechanical properties of well-defined polyethylene-graft-poly(n-butyl acrylate) prepared by atom transfer radical polymerization , 2004 .

[9]  K. Matyjaszewski,et al.  Simple and effective one-pot synthesis of (meth)acrylic block copolymers through atom transfer radical polymerization , 2000 .

[10]  H. Höcker,et al.  A Novel Macroinitiator for the Synthesis of Triblock Copolymers via Atom Transfer Radical Polymerization: Polystyrene-block-poly(bisphenol A carbonate)-block-polystyrene and Poly(methyl methacrylate)-block-poly(bisphenol A carbonate)-block-poly(methyl methacrylate) , 2004 .

[11]  K. Matyjaszewski,et al.  Controlled/living radical polymerization in aqueous media: homogeneous and heterogeneous systems , 2001 .

[12]  D. Bertin,et al.  Living Character of Polymer Chains Prepared via Nitroxide-Mediated Controlled Free-Radical Polymerization of Methyl Methacrylate in the Presence of a Small Amount of Styrene at Low Temperature , 2006 .

[13]  K. Matyjaszewski,et al.  Measurement of Initial Degree of Polymerization without Reactivation as a New Method To Estimate Rate Constants of Deactivation in ATRP , 2002 .

[14]  Matyjaszewski.  Radical Nature of Cu-Catalyzed Controlled Radical Polymerizations (Atom Transfer Radical Polymerization). , 1998, Macromolecules.

[15]  K. Matyjaszewski,et al.  Polymerization of Substituted Styrenes by Atom Transfer Radical Polymerization , 1997 .

[16]  A. Studer,et al.  New Sterically Hindered Nitroxides for the Living Free Radical Polymerization: X-ray Structure of an α-H-Bearing Nitroxide , 2004 .

[17]  V. Percec,et al.  Metal-Catalyzed “Living” Radical Polymerization of Styrene Initiated with Arenesulfonyl Chlorides. From Heterogeneous to Homogeneous Catalysis , 1996 .

[18]  Krzysztof Matyjaszewski,et al.  Inverse miniemulsion ATRP: a new method for synthesis and functionalization of well-defined water-soluble/cross-linked polymeric particles. , 2006, Journal of the American Chemical Society.

[19]  Shiping Zhu,et al.  Synthesis of methacrylate macromonomers using silica gel supported atom transfer radical polymerization , 2000 .

[20]  K. Matyjaszewski,et al.  Activator Generated by Electron Transfer for Atom Transfer Radical Polymerization , 2005 .

[21]  T. Fukuda,et al.  Nitroxide-controlled free-radical copolymerization of vinyl and divinyl monomers. Evaluation of pendant-vinyl reactivity , 1997 .

[22]  Michael J. Ziegler,et al.  Atom Transfer Radical Copolymerization of Methyl Methacrylate and n-Butyl Acrylate , 2001 .

[23]  G. Koten,et al.  Diaminoarylnickel(II) “Pincer” Complexes: Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts , 1998 .

[24]  Krzysztof Matyjaszewski,et al.  Macromolecular engineering: From rational design through precise macromolecular synthesis and processing to targeted macroscopic material properties , 2005 .

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

[26]  David H. Solomon,et al.  The Chemistry of Radical Polymerization , 2005 .

[27]  Krzysztof Matyjaszewski,et al.  Macromolecular engineering : precise synthesis, materials properties, applications , 2007 .

[28]  Gordon K. Hamer,et al.  Narrow molecular weight resins by a free-radical polymerization process , 1993 .

[29]  I. Hirono.  A Comparative Study of the Mode of Action of X-Rays and Alkylating Agents , 1955, Nature.

[30]  K. Matyjaszewski,et al.  Synthesis of Degradable Miktoarm Star Copolymers via Atom Transfer Radical Polymerization , 2005 .

[31]  T. Satoh,et al.  Atom Transfer Radical Polymerization of Methyl Methacrylate in Fluoroalcohol: Simultaneous Control of Molecular Weight and Tacticity , 2005 .

[32]  K. Matyjaszewski,et al.  Structural Control in ATRP Synthesis of Star Polymers Using the Arm-First Method , 2006 .

[33]  K. Matyjaszewski,et al.  Effect of Initiation Conditions on the Uniformity of Three-Arm Star Molecular Brushes , 2003 .

[34]  C. Brochon,et al.  Macromolecular Design via the Interchange of Xanthates (MADIX): Polymerization of Styrene with O‐Ethyl Xanthates as Controlling Agents , 2002 .

[35]  T. Otsu.  Iniferter concept and living radical polymerization , 2000 .

[36]  D. Solomon.  Genesis of the CSIRO polymer group and the discovery and significance of nitroxide‐mediated living radical polymerization , 2005 .

[37]  R. Gil,et al.  Synthesis of Hydroxy-Telechelic Poly(methyl acrylate) and Polystyrene by Atom Transfer Radical Coupling , 2004 .

[38]  K. Matyjaszewski,et al.  Halide Anions as Ligands in Iron-Mediated Atom Transfer Radical Polymerization , 2000 .

[39]  K. Matyjaszewski,et al.  Effect of Penultimate Unit on the Activation Process in ATRP , 2003 .

[40]  A. Deydier,et al.  Influence of Coordination Geometry upon Copper(II/I) Redox Potentials. Physical Parameters for Twelve Copper Tripodal Ligand Complexes , 1999 .

[41]  Graeme Moad,et al.  Living free radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization): Approaches to star polymers , 2003 .

[42]  Michael J. Ziegler,et al.  Gradient copolymers by atom transfer radical copolymerization , 2000 .

[43]  K. Matyjaszewski,et al.  Synthesis of Molecular Brushes with Gradient in Grafting Density by Atom Transfer Polymerization , 2002 .

[44]  S. Maria,et al.  An experimental and computational study on the effect of Al(OiPr)3 on atom-transfer radical polymerization and on the catalyst-dormant-chain halogen exchange. , 2005, Chemistry.

[45]  K. Matyjaszewski,et al.  New amine-based tripodal copper catalysts for atom transfer radical polymerization , 2004 .

[46]  A. Matsumoto,et al.  Features of living radical polymerization of vinyl monomers in homogeneous system using N,N-diethyldithiocarbamate derivatives as photoiniferters , 1995 .

[47]  Krzysztof Matyjaszewski,et al.  Preparation of Polyacrylonitrile-block-poly(n-butyl acrylate) Copolymers Using Atom Transfer Radical Polymerization and Nitroxide Mediated Polymerization Processes , 2003 .

[48]  K. Matyjaszewski,et al.  Structural Control of Poly(methyl methacrylate)-g-poly(dimethylsiloxane) Copolymers Using Controlled Radical Polymerization: Effect of the Molecular Structure on Morphology and Mechanical Properties , 2003 .

[49]  L. Radom,et al.  The reversible addition-fragmentation chain transfer process and the strength and limitations of modeling: Comment on “the magnitude of the fragmentation rate coefficient” , 2003 .

[50]  Shiping Zhu,et al.  Atom Transfer Radical Polymerization of Methyl Methacrylate by Silica Gel Supported Copper Bromide/Multidentate Amine , 2000 .

[51]  C. Hawker,et al.  Synthesis of poly(olefin) graft copolymers by a combination of metallocene and living free radical polymerization techniques , 1998 .

[52]  K. Matyjaszewski,et al.  AGET ATRP in the Presence of Air in Miniemulsion and in Bulk , 2006 .

[53]  J. Chiefari,et al.  Tailored polymer architectures by reversible addition‐frasmentation chain transfer , 2001 .

[54]  K. Matyjaszewski,et al.  Removal of Copper-Based Catalyst in Atom Transfer Radical Polymerization Using Ion Exchange Resins , 2000 .

[55]  K. Matyjaszewski,et al.  Fundamentals of Supported Catalysts for Atom Transfer Radical Polymerization (ATRP) and Application of an Immobilized/Soluble Hybrid Catalyst System to ATRP , 2002 .

[56]  M. Szwarc,et al.  Reactions of Methyl Radicals with Substrates Acting as Hydrogen Donors and as Methyl Radical Acceptors , 1956 .

[57]  M. Sawamoto,et al.  Nickel-Mediated Living Radical Polymerization of Methyl Methacrylate1 , 1997 .

[58]  K. Matyjaszewski,et al.  Effect of [CuII] on the Rate of Activation in ATRP , 2005 .

[59]  M. Sawamoto,et al.  Re(V)-Mediated Living Radical Polymerization of Styrene:1 ReO2I(PPh3)2/R−I Initiating Systems , 1999 .

[60]  A. Sehon,et al.  The C-Br Bond Dissociation Energy in Benzyl Bromide and Allyl Bromide , 1950 .

[61]  K. Matyjaszewski,et al.  Determination of Rate Constants for the Activation Step in Atom Transfer Radical Polymerization Using the Stopped-Flow Technique , 2004 .

[62]  M. Sawamoto,et al.  Iron(II) Chloride Complex for Living Radical Polymerization of Methyl Methacrylate1 , 1997 .

[63]  M. Radosz,et al.  CuBr2/N,N,N',N'-tetra[(2-pyridal)methyl] ethylenediamine/tertiary amine as a highly active and versatile catalyst for atom-transfer radical polymerization via activator generated by electron transfer , 2006 .

[64]  K. Matyjaszewski,et al.  Determination of equilibrium constants for atom transfer radical polymerization. , 2006, Journal of the American Chemical Society.

[65]  Krzysztof Matyjaszewski,et al.  Controlled Radical Polymerization by Degenerative Transfer - Effect of the Structure of the Transfer Agent , 1995 .

[66]  D. Gigmes,et al.  Factors influencing C-ON bond homolysis in alkoxyamines: unexpected behavior of SG1 (N-(2-methyl-2-propyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl)-based alkoxyamines. , 2004, The Journal of organic chemistry.

[67]  M. Lansalot,et al.  Controlled Free-Radical Miniemulsion Polymerization of Styrene Using Degenerative Transfer , 1999 .

[68]  D. Haddleton,et al.  Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by Alkyl Bromide and 2-Pyridinecarbaldehyde Imine Copper(I) Complexes , 1997 .

[69]  Y. K. Chong,et al.  Thiocarbonylthio Compounds [SC(Ph)S−R] in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Role of the Free-Radical Leaving Group (R) , 2003 .

[70]  M. Imoto.  Theory of radical polymerization. , 1987 .

[71]  K. Matyjaszewski,et al.  The Effect of Ligands on Copper-Mediated Atom Transfer Radical Polymerization , 2000 .

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

[73]  K. Matyjaszewski,et al.  Synthesis and ATRP activity of new tren-based ligands , 2004 .

[74]  S. Kobatake,et al.  Block Copolymer Synthesis by Styrene Polymerization Initiated with Nitroxy-Functionalized Polybutadiene , 1998 .

[75]  K. Matyjaszewski,et al.  Rational Selection of Initiating/Catalytic Systems for the Copper-Mediated Atom Transfer Radical Polymerization of Basic Monomers in Protic Media: ATRP of 4-Vinylpyridine , 2006 .

[76]  K. Matyjaszewski,et al.  Block copolymers by transformation of living ring-opening metathesis polymerization into controlled/living atom transfer radical polymerization , 1997 .

[77]  E. Harth,et al.  Chain End Functionalization in Nitroxide-Mediated “Living” Free Radical Polymerizations , 2001 .

[78]  M. Charreyre,et al.  Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process , 2006 .

[79]  R. Poli.  Relationship between one-electron transition-metal reactivity and radical polymerization processes. , 2006, Angewandte Chemie.

[80]  K. Matyjaszewski,et al.  Homogeneous Reverse Atom Transfer Radical Polymerization of Styrene Initiated by Peroxides , 1999 .

[81]  K. Matyjaszewski,et al.  Poly[N-(2-hydroxypropyl)methacrylamide-block-n-butyl acrylate] micelles in water/DMF mixed solvents , 2002 .

[82]  B. Baird,et al.  Antigen-decorated shell cross-linked nanoparticles: synthesis, characterization, and antibody interactions. , 2005, Bioconjugate chemistry.

[83]  K. Matyjaszewski,et al.  Unified approach to living and non-living cationic polymerization of alkenes , 1994 .

[84]  Almar Postma,et al.  Living free radical polymerization with reversible addition : fragmentation chain transfer (the life of RAFT) , 2000 .

[85]  K. Matyjaszewski,et al.  Reversible collapse of brushlike macromolecules in ethanol and water vapours as revealed by real-time scanning force microscopy. , 2004, Chemistry.

[86]  M. Charton.  Electrical Effect Substituent Constants for Correlation Analysis , 2007 .

[87]  K. Matyjaszewski,et al.  Formation of Block Copolymers by Transformation of Cationic Ring-Opening Polymerization to Atom Transfer Radical Polymerization (ATRP) , 1998 .

[88]  T. Fukuda,et al.  Rate Retardation in Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization: Further Evidence for Cross-Termination Producing 3-Arm Star Chain , 2004 .

[89]  K. Matyjaszewski,et al.  Preparation of gradient copolymers via ATRP using a simultaneous reverse and normal initiation process. I. Spontaneous gradient , 2005 .

[90]  K. Matyjaszewski,et al.  Amphiphilic block copolymers prepared via controlled radical polymerization as surfactants for emulsion polymerization , 2000 .

[91]  K. Matyjaszewski,et al.  Synthesis of Acrylate and Methacrylate Block Copolymers Using Atom Transfer Radical Polymerization , 1998 .

[92]  K. A. Davis,et al.  Observation and analysis of a slow termination process in the atom transfer radical polymerization of styrene , 1997 .

[93]  K. Matyjaszewski,et al.  Deactivation efficiency and degree of control over polymerization in ATRP in protic solvents , 2004 .

[94]  J. Hedrick,et al.  Living free radical polymerization of macromonomers : preparation of well defined graft copolymers , 1997 .

[95]  T. Fukuda,et al.  Nitroxide-controlled free-radical copolymerization of vinyl and divinyl monomers. 2. Gelation , 1999 .

[96]  Yoshio Okamoto,et al.  Xanthate-Mediated Radical Polymerization of N-Vinylpyrrolidone in Fluoroalcohols for Simultaneous Control of Molecular Weight and Tacticity , 2005 .

[97]  W. Brittain,et al.  Use of JandaJel Resins for Copper Removal in Atom Transfer Radical Polymerization , 2003 .

[98]  K. Matyjaszewski.  Cationic polymerizations : mechanisms, synthesis, and applications , 1996 .

[99]  K. Matyjaszewski,et al.  Exchange reactions in the living cationic polymerization of alkenes , 1991 .

[100]  S. D. Ittel,et al.  Catalytic chain transfer in free-radical polymerizations. , 2001, Chemical reviews.

[101]  S. Yamago.  Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions , 2006 .

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

[103]  A. Fürstner,et al.  Nozaki−Hiyama−Kishi Reactions Catalytic in Chromium , 1996 .

[104]  K. Matyjaszewski,et al.  End-Functional Poly(tert-butyl acrylate) Star Polymers by Controlled Radical Polymerization , 2000 .

[105]  M. Monteiro,et al.  Intermediate radical termination as the mechanism for retardation in reversible addition-fragmentation chain transfer polymerization , 2001 .

[106]  C. Barner‐Kowollik,et al.  Modeling the reversible addition–fragmentation chain transfer process in cumyl dithiobenzoate‐mediated styrene homopolymerizations: Assessing rate coefficients for the addition–fragmentation equilibrium , 2001 .

[107]  K. Matyjaszewski,et al.  Block copolymers by transformation of living anionic polymerization into controlled/“living” atom transfer radical polymerization , 1999 .

[108]  K. Matyjaszewski,et al.  ATRP of butyl acrylates from functionalized carbon black surfaces , 2005 .

[109]  Krzysztof Matyjaszewski,et al.  Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes , 1995 .

[110]  K. Matyjaszewski,et al.  Copper-based ATRP catalysts of very high activity derived from dimethyl cross-bridged cyclam , 2006 .

[111]  S. Armes,et al.  First example of the atom transfer radical polymerisation of an acidic monomer: direct synthesis of methacrylic acid copolymers in aqueous media , 1999 .

[112]  J. Nicolas,et al.  Nitroxide-Mediated Controlled Free-Radical Emulsion Polymerization Using a Difunctional Water-Soluble Alkoxyamine Initiator. Toward the Control of Particle Size, Particle Size Distribution, and the Synthesis of Triblock Copolymers , 2005 .

[113]  K. Matyjaszewski.  Inner sphere and outer sphere electron transfer reactions in atom transfer radical polymerization , 1998 .

[114]  F. Minisci.  Free-radical additions to olefins in the presence of redox systems , 1975 .

[115]  K. Matyjaszewski,et al.  Controlled/“Living” Radical Polymerization. Atom Transfer Radical Polymerization Catalyzed by Copper(I) and Picolylamine Complexes , 1999 .

[116]  B. Klumperman,et al.  Effect of Solvent on the Activation Rate Parameters for Polystyrene and Poly(butyl acrylate) Macroinitiators in Atom Transfer Radical Polymerization , 2000 .

[117]  K. Matyjaszewski,et al.  Zerovalent Metals in Controlled/“Living” Radical Polymerization , 1997 .

[118]  K. Matyjaszewski,et al.  Complex nanostructured materials from segmented copolymers prepared by ATRP , 2003, The European physical journal. E, Soft matter.

[119]  K. Matyjaszewski,et al.  Activators regenerated by electron transfer for atom-transfer radical polymerization of (meth)acrylates and related block copolymers. , 2006, Angewandte Chemie.

[120]  K. Matyjaszewski,et al.  Evaluation of acrylate-based block copolymers prepared by atom transfer radical polymerization as matrices for paclitaxel delivery from coronary stents. , 2005, Biomacromolecules.

[121]  K. Matyjaszewski,et al.  Synthesis of Well-Defined Polyacrylonitrile by Atom Transfer Radical Polymerization , 1997 .

[122]  C. Walling.  Free Radicals In Solution , 1957 .

[123]  Shiping Zhu,et al.  A difference of six orders of magnitude: A reply to “the magnitude of the fragmentation rate coefficient” , 2003 .

[124]  K. Matyjaszewski,et al.  Effect of [bpy]/[Cu(I)] ratio, solvent, counterion, and alkyl bromides on the activation rate constants in atom transfer radical polymerization , 2003 .

[125]  A. Demonceau,et al.  Highly Efficient Ruthenium-Based Catalytic Systems for the Controlled Free-Radical Polymerization of Vinyl Monomers. , 1999, Angewandte Chemie.

[126]  K. Matyjaszewski,et al.  Measuring molecular weight by atomic force microscopy. , 2003, Journal of the American Chemical Society.

[127]  V. Percec,et al.  Synthesis of poly(vinyl chloride)‐b‐poly(2‐ethylhexyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of vinyl chloride initiated from α,ω‐di(iodo)poly(2‐ethylhexyl acrylate) and catalyzed with sodium dit , 2005 .

[128]  Zi‐Chen Li,et al.  Synthesis of Alternating Copolymers of N-Substituted Maleimides with Styrene via Atom Transfer Radical Polymerization , 2000 .

[129]  Huadong Tang,et al.  Catalyst separation in atom transfer radical polymerization , 2004 .

[130]  R. Jerome,et al.  Highly efficient cobalt-mediated radical polymerization of vinyl acetate. , 2005, Angewandte Chemie.

[131]  Krzysztof Matyjaszewski,et al.  Effect of ligand structure on activation rate constants in ATRP , 2006 .

[132]  J. D. Druliner.  Living radical polymerization involving oxygen-centered species attached to propagating chain ends , 1991 .

[133]  B. Wayland,et al.  Control of Radical Polymerizations by Metalloradicals , 1998 .

[134]  K. Matyjaszewski,et al.  Simultaneous EPR and Kinetic Study of Styrene Atom Transfer Radical Polymerization (ATRP) , 1998 .

[135]  D. Greszta,et al.  "Living" radical polymerization. 1. Possibilities and limitations , 1994 .

[136]  Brian S. Hawkett,et al.  Ab initio emulsion polymerization by RAFT-controlled self-assembly , 2005 .

[137]  T. Fukuda,et al.  Effects of Radical Initiator on Polymerization Rate and Polydispersity in Nitroxide-Controlled Free Radical Polymerization , 1997 .

[138]  J. Krstina,et al.  Narrow Polydispersity Block Copolymers by Free-Radical Polymerization in the Presence of Macromonomers , 1995 .

[139]  K. Matyjaszewski,et al.  Ion ⇄ ester equilibria in the living cationic polymerization of tetrahydrofuran , 1974 .

[140]  S. Maria,et al.  The radical trap in atom transfer radical polymerization need not be thermodynamically stable. A study of the MoX(3)(PMe(3))(3) catalysts. , 2005, Journal of the American Chemical Society.

[141]  D. Sherrington,et al.  Synthesis of highly branched poly(methyl methacrylate)s using the 'strathclyde methodology' in aqueous emulsion , 2006 .

[142]  K. Matyjaszewski,et al.  Improving the Structural Control of Graft Copolymers. Copolymerization of Poly(dimethylsiloxane) Macromonomer with Methyl Methacrylate Using RAFT Polymerization , 2001 .

[143]  Krzysztof Matyjaszewski,et al.  Controlled/“Living” Radical Polymerization. Kinetics of the Homogeneous Atom Transfer Radical Polymerization of Styrene , 1997 .

[144]  J. Lingane.  Interpretation of the Polarographic Waves of Complex Metal Ions. , 1941 .

[145]  M. Rogers,et al.  Cross-bridged cyclam. Protonation and lithium cation (Li+) complexation in a diamond-lattice cleft , 1990 .

[146]  M. Becker,et al.  Peptide-polymer bioconjugates: hybrid block copolymers generated via living radical polymerizations from resin-supported peptides. , 2003, Chemical communications.

[147]  K. Matyjaszewski,et al.  Synthesis of block and graft copolymers with linear polyethylene segments by combination of degenerative transfer coordination polymerization and atom transfer radical polymerization , 2005 .

[148]  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.

[149]  L. Bronstein,et al.  Atom Transfer Radical Polymerization with Ti(III) Halides and Alkoxides , 2003 .

[150]  K. Matyjaszewski,et al.  Kinetics of decomposition of 2,2,6,6-tetramethyl-1-(1-phenylethoxy)piperidine and its implications on nitroxyl-mediated styrene polymerization , 1995 .

[151]  K. Matyjaszewski,et al.  Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents , 2006, Proceedings of the National Academy of Sciences.

[152]  H. Cohen,et al.  Design of Ligands That Stabilize Cu(I) and Shift the Reduction Potential of the Cu(II/I) Couple Cathodically in Aqueous Solutions. , 1999, Inorganic chemistry.

[153]  Keda Zhang,et al.  Novel catalyst system of MCl2/FeCl3·6H2O/PPh3 (M = Ni, Co, or Mn) for the atom transfer radical polymerization of methyl methacrylate , 2005 .

[154]  Y. Gan,et al.  Ultra high molar mass poly[2-(dimethylamino)ethyl methacrylate] via atom transfer radical polymerization , 2006 .

[155]  B. Wayland,et al.  Degenerative Transfer and Reversible Termination Mechanisms for Living Radical Polymerizations Mediated by Cobalt Porphyrins , 2006 .

[156]  S. Zard,et al.  The Degenerative Radical Transfer of Xanthates and Related Derivatives: An Unusually Powerful Tool for the Creation of Carbon—Carbon Bonds , 2007 .

[157]  V. Percec,et al.  Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride. , 2002, Journal of the American Chemical Society.

[158]  J. Fréchet.  Functional polymers: from plastic electronics to polymer-assisted therapeutics , 2005 .

[159]  Leland C. Burrill,et al.  Low-temperature preparations of unimolecular nitroxide initiators for living free radical polymerizations , 1997 .

[160]  Catherine L. Moad,et al.  Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers , 1996 .

[161]  T. Nakano,et al.  Stereocontrol in radical polymerization of acrylic monomers , 2002 .

[162]  K. Matyjaszewski,et al.  Controlled/Living Radical Polymerization of Vinyl Acetate by Degenerative Transfer with Alkyl Iodides , 2003 .

[163]  A. Clark.  Atom transfer radical cyclisation reactions mediated by copper complexes. , 2002, Chemical Society reviews.

[164]  H. Maynard,et al.  Cysteine-reactive polymers synthesized by atom transfer radical polymerization for conjugation to proteins. , 2004, Journal of the American Chemical Society.

[165]  W. I. Bengough,et al.  Effects of salts of metals on vinyl polymerization. Part 1.—Polymerization of methyl methacrylate in presence of cupric chloride , 1965 .

[166]  Sébastien Perrier,et al.  Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization , 2005 .

[167]  K. Matyjaszewski,et al.  Immobilization of the Copper Catalyst in Atom Transfer Radical Polymerization , 1999 .

[168]  C. Barner‐Kowollik,et al.  Quantum chemical mapping of initialization processes in RAFT polymerization , 2006 .

[169]  K. Matyjaszewski,et al.  Reevaluation of Persistent Radical Effect in NMP , 2006 .

[170]  K. Matyjaszewski,et al.  Comparison of bond dissociation energies of dormant species relevant to degenerative transfer and atom transfer radical polymerization , 2005 .

[171]  Stuart W. Prescott,et al.  Successful Use of RAFT Techniques in Seeded Emulsion Polymerization of Styrene: Living Character, RAFT Agent Transport, and Rate of Polymerization , 2002 .

[172]  P. Dubois,et al.  Alternative Atom Transfer Radical Polymerization for MMA Using FeCl3 and AIBN in the Presence of Triphenylphosphine: An Easy Way to Well-Controlled PMMA† , 1998 .

[173]  K. Matyjaszewski,et al.  Graft Copolymers from Linear Polyethylene via Atom Transfer Radical Polymerization , 2004 .

[174]  K. Matyjaszewski,et al.  Preparation of polyisobutene-graft-poly(methyl methacrylate) and polyisobutene-graft-polystyrene with different compositions and side chain architectures through atom transfer radical polymerization (ATRP) , 2001 .

[175]  K. Matyjaszewski,et al.  Controlled/living radical polymerization. Atom transfer radical polymerization using multidentate amine ligands , 1997 .

[176]  K. Matyjaszewski,et al.  The macroester ⇄ macroion equilibrium in the cationic polymerization of THF observed directly by 300 MHz1 H NMR , 1974 .

[177]  P. Dubois,et al.  Controlled Radical Polymerization of Methyl Methacrylate in the Presence of Palladium Acetate, Triphenylphosphine, and Carbon Tetrachloride , 1997 .

[178]  B. Yamada,et al.  Radical polymerization of styrene mediated by 1,3,5-triphenylverdazyl , 1998 .

[179]  J. Nicolas,et al.  Novel SG1-Based Water-Soluble Alkoxyamine for Nitroxide-Mediated Controlled Free-Radical Polymerization of Styrene and n-Butyl Acrylate in Miniemulsion , 2004 .

[180]  V. Percec,et al.  Metal‐catalyzed living radical graft copolymerization of olefins initiated from the structural defects of poly(vinyl chloride) , 2001 .

[181]  G. Koten,et al.  Controlled radical polymerization of styrene in the presence of lithium molybdate(V) complexes and benzylic halides , 1999 .

[182]  Daniel C. Hill,et al.  Synthesis and Characterization of Cross-Bridged Cyclams and Pendant-Armed Derivatives and Structural Studies of Their Copper(II) Complexes , 2000 .

[183]  L. Leibler.  Nanostructured plastics: Joys of self-assembling , 2005 .

[184]  K. Baek,et al.  Possibility of Living Radical Polymerization of Vinyl Acetate Catalyzed by Iron(I) Complex1 , 2002 .

[185]  Takeshi Fukuda,et al.  Kinetics of Living Radical Polymerization , 2004 .

[186]  K. Matyjaszewski.  The synthesis of functional star copolymers as an illustration of the importance of controlling polymer structures in the design of new materials , 2003 .

[187]  C. Detrembleur,et al.  Effective cobalt mediation of the radical polymerization of vinyl acetate in suspension. , 2005, Angewandte Chemie.

[188]  Krzysztof Matyjaszewski,et al.  Synthesis of branched and hyperbranched polystyrenes , 1996 .

[189]  M. Sawamoto,et al.  RAFT Polymerization of N-Isopropylacrylamide in the Absence and Presence of Y(OTf)3: Simultaneous Control of Molecular Weight and Tacticity , 2004 .

[190]  D. Taton,et al.  Atom transfer radical polymerization of styrene using a novel octafunctional initiator : Synthesis of well-defined polystyrene stars , 1998 .

[191]  C. Barner‐Kowollik,et al.  Long‐lived intermediates in reversible addition–fragmentation chain‐transfer (RAFT) polymerization generated by γ radiation , 2002 .

[192]  K. A. Davis,et al.  Effect of (Pseudo)halide Initiators and Copper Complexes with Non‐halogen Anions on the Atom Transfer Radical Polymerization , 2004 .

[193]  M. Szwarc.  |[lsquo]|Living|[rsquo]| Polymers , 1956 .

[194]  K. Matyjaszewski,et al.  Super soft elastomers as ionic conductors , 2004 .

[195]  K. Matyjaszewski,et al.  Environmentally benign atom transfer radical polymerization: Towards “green” processes and materials , 2006 .

[196]  Krzysztof Matyjaszewski,et al.  Controlled/“Living” Radical Polymerization. Homogeneous Reverse Atom Transfer Radical Polymerization Using AIBN as the Initiator , 1997 .

[197]  K. Matyjaszewski,et al.  RAFT Polymerization of Acrylonitrile and Preparation of Block Copolymers Using 2-Cyanoethyl Dithiobenzoate as the Transfer Agent , 2003 .

[198]  C. Hawker,et al.  Initiating Systems for Nitroxide-Mediated ``Living'' Free Radical Polymerizations: Synthesis and Evaluation , 1996 .

[199]  Krzysztof Matyjaszewski,et al.  An Investigation into the CuX/2,2‘-Bipyridine (X = Br or Cl) Mediated Atom Transfer Radical Polymerization of Acrylonitrile , 1999 .

[200]  K. Matyjaszewski,et al.  HALOGEN EXCHANGE IN ATOM TRANSFER RADICAL POLYMERIZATION AS A ROUTE TO WELL-DEFINED BLOCK COPOLYMERS , 2005 .

[201]  J. Kennedy,et al.  Designed Polymers by Carbocationic Macromolecular Engineering , 1992 .

[202]  B. Klumperman,et al.  Experimental Determination of the Rate Constant of Deactivation of Poly(styrene) and Poly(butyl acrylate) Radicals in Atom Transfer Radical Polymerization , 2002 .

[203]  K. Matyjaszewski.  Controlled/living radical polymerization : State of the art in 2005 , 2003 .

[204]  K. Matyjaszewski,et al.  Controlled/“Living” Radical Polymerization of Styrene and Methyl Methacrylate Catalyzed by Iron Complexes1 , 1997 .

[205]  Krzysztof Matyjaszewski,et al.  Synthesis of Nanocomposite Organic/Inorganic Hybrid Materials Using Controlled/“Living” Radical Polymerization , 2001 .

[206]  E. Yoshida,et al.  Synthesis of Poly(tetrahydrofuran) with a Nitroxyl Radical at the Chain End and Its Application to Living Radical Polymerization , 1996 .

[207]  Krzysztof Matyjaszewski,et al.  Polystyrene with designed molecular weight distribution by atom transfer radical coupling , 2004 .

[208]  K. Matyjaszewski,et al.  Tadpole Conformation of Gradient Polymer Brushes , 2004 .

[209]  R. Gil,et al.  Quantifying Vinyl Monomer Coordination to CuI in Solution and the Effect of Coordination on Monomer Reactivity in Radical Copolymerization , 2005 .

[210]  M. Sawamoto,et al.  Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization , 1995 .

[211]  K. Matyjaszewski,et al.  Functional polymers by atom transfer radical polymerization , 2001 .

[212]  K. Matyjaszewski,et al.  Hydrogels by atom transfer radical polymerization. I. Poly(N-vinylpyrrolidinone-g-styrene) via the macromonomer method , 1998 .

[213]  K. Matyjaszewski.  Controlled radical polymerization , 1996 .

[214]  M. Arshadi,et al.  Hydration of the halide negative ions in the gas phase. II. Comparison of hydration energies for the alkali positive and halide negative ions , 1970 .

[215]  M. Thelakkat,et al.  Nanostructures of n-Type Organic Semiconductor in a p-Type Matrix via Self-Assembly of Block Copolymers , 2004 .

[216]  K. Matyjaszewski,et al.  Structural Control of Poly(Methyl Methacrylate)-g-poly(Lactic Acid) Graft Copolymers by Atom Transfer Radical Polymerization (ATRP) , 2001 .

[217]  B. Wayland,et al.  Living Radical Polymerization of Acrylates by Organocobalt Porphyrin Complexes , 1994 .

[218]  M. Szwarc,et al.  Effect of Conjugation, Hyperconjugation, and Steric Hindrance on Methyl Affinities , 1959 .

[219]  J. Kennedy,et al.  Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice , 1992 .

[220]  K. Kirshenbaum,et al.  New applications of catalytic chain transfer polymerization to waterborne binders for automotive paint systems , 2002 .

[221]  J. Chiefari,et al.  Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process , 1998 .

[222]  Krzysztof Matyjaszewski,et al.  The Synthesis of Densely Grafted Copolymers by Atom Transfer Radical Polymerization , 1998 .

[223]  D. Gigmes,et al.  Polar, Steric, and Stabilization Effects in Alkoxyamines C−ON Bond Homolysis: A Multiparameter Analysis , 2005 .

[224]  Krzysztof Matyjaszewski,et al.  Controlled/Living Radical Polymerization , 2005 .

[225]  K. Matyjaszewski,et al.  Synthesis of Star-Shaped Polystyrene by Atom Transfer Radical Polymerization Using an “Arm First” Approach , 1999 .

[226]  J. Yoshida,et al.  Mechanism-based invention of high-speed living radical polymerization using organotellurium compounds and azo-initiators. , 2003, Journal of the American Chemical Society.

[227]  A. Vlček.  Polarographic Behavior of Coordination Compounds , 2007 .

[228]  K. Matyjaszewski,et al.  Effect of [PMDETA]/[Cu(I)] Ratio, Monomer, Solvent, Counterion, Ligand, and Alkyl Bromide on the Activation Rate Constants in Atom Transfer Radical Polymerization , 2003 .

[229]  K. Matyjaszewski,et al.  Synthesis of poly(2-hydroxyethyl methacrylate) in protic media through atom transfer radical polymerization using activators generated by electron transfer , 2006 .

[230]  K. Matyjaszewski,et al.  Activators Regenerated by Electron Transfer for Atom Transfer Radical Polymerization of Styrene , 2006 .

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

[232]  K. Matyjaszewski,et al.  Densely-Grafted and Double-Grafted PEO Brushes via ATRP. A Route to Soft Elastomers , 2003 .

[233]  T. Fukuda,et al.  Structure and properties of high-density polymer brushes prepared by surface-initiated living radical polymerization , 2006 .

[234]  J. Chiefari,et al.  Thiocarbonylthio Compounds (SC(Z)S−R) in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Effect of the Activating Group Z , 2003 .

[235]  M. Coote,et al.  Is the addition-fragmentation step of the RAFT polymerisation process chain length dependent? , 2006 .

[236]  K. Matyjaszewski,et al.  Radical (Co)polymerization of vinyl chloroacetate and N-vinylpyrrolidone mediated by Bis(acetylacetonate)cobalt derivatives , 2006 .

[237]  T. Fukuda,et al.  Mechanism and Kinetics of Organostibine-Mediated Living Radical Polymerization of Styrene , 2005 .

[238]  K. Matyjaszewski,et al.  Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization , 2000 .

[239]  Charles R. Chambers,et al.  Recent advances in resists for 157 nm microlithography , 2002 .

[240]  D. Belluš.  Copper-catalyzed additions of organic polyhalides to olefins: a versatile synthetic tool , 1985 .

[241]  Craig J. Hawker,et al.  Molecular Weight Control by a "Living" Free-Radical Polymerization Process , 1994 .

[242]  Masatoshi Yoshida,et al.  A model for living radical polymerization , 1982 .

[243]  C. Barner‐Kowollik,et al.  Origin of Inhibition Effects in the Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate , 2002 .

[244]  Jean M. J. Fréchet,et al.  A Tandem Approach to Graft and Dendritic Graft Copolymers Based on “Living” Free Radical Polymerizations† , 1997 .

[245]  K. Matyjaszewski,et al.  Polymerization of n-Butyl Acrylate by Atom Transfer Radical Polymerization. Remarkable Effect of Ethylene Carbonate and Other Solvents , 1998 .

[246]  Ying Mei,et al.  Solid-phase ATRP synthesis of peptide-polymer hybrids. , 2004, Journal of the American Chemical Society.

[247]  K. Matyjaszewski,et al.  Synthesis of block, graft and star polymers from inorganic macroinitiators , 1998 .

[248]  K. Matyjaszewski,et al.  Atom Transfer Radical Copolymerization of Styrene and n-Butyl Acrylate , 1999 .

[249]  K. Matyjaszewski,et al.  Controlled/“Living” Radical Polymerization. Atom Transfer Radical Polymerization of Acrylates at Ambient Temperature , 1998 .

[250]  M. Szwarc,et al.  Determination of Some Carbon‐Chlorine Bond Dissociation Energies , 1954 .

[251]  Krzysztof Matyjaszewski,et al.  Synthesis of Star Polymers by a Combination of ATRP and the “Click” Coupling Method , 2006 .

[252]  K. Matyjaszewski,et al.  Synthesis of well-defined block copolymers tethered to polysilsesquioxane nanoparticles and their nanoscale morphology on surfaces. , 2001, Journal of the American Chemical Society.

[253]  Woodworth,et al.  Interaction of Propagating Radicals with Copper(I) and Copper(II) Species. , 1998, Macromolecules.

[254]  D. Busch,et al.  Synthesis, structure, and stability in acid of copper(II) and zinc(II) complexes of cross-bridged tetraazamacrocycles , 2003 .

[255]  K. Matyjaszewski,et al.  Preparation of Linear and Star-Shaped Block Copolymers by ATRP Using Simultaneous Reverse and Normal Initiation Process in Bulk and Miniemulsion , 2004 .

[256]  Herbert Mayr,et al.  Nucleophilie‐ und Elektrophilieskalen als Ordnungsprinzipien polarer organischer und metallorganischer Reaktionen , 1994 .

[257]  H. Klok.  Biological-synthetic hybrid block copolymers: Combining the best from two worlds , 2005 .

[258]  J. Durrant,et al.  The mechanism of the addition of tetrahaloalkanes to alkenes in the presence of RuCl2(PPh3)3 , 1984 .

[259]  K. Matyjaszewski,et al.  Synthesis of Block, Statistical, and Gradient Copolymers from Octadecyl (Meth)acrylates Using Atom Transfer Radical Polymerization , 2003 .

[260]  C. Barner‐Kowollik,et al.  Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation , 2006 .

[261]  M. Coote.  Ab Initio Study of the Addition−Fragmentation Equilibrium in RAFT Polymerization: When Is Polymerization Retarded? , 2004 .

[262]  Scott M. Grayson,et al.  An efficient route to well-defined macrocyclic polymers via "click" cyclization. , 2006, Journal of the American Chemical Society.

[263]  Amy C. Gottfried,et al.  Polyolefin graft copolymers via living polymerization techniques: Preparation of poly(n‐butyl acrylate)‐graft‐polyethylene through the combination of Pd‐mediated living olefin polymerization and atom transfer radical polymerization , 2002 .

[264]  R. Quirk,et al.  Anionic Polymerization: Principles and Practical Applications , 1996 .

[265]  K. Matyjaszewski,et al.  Structural aspects of copper catalyzed atom transfer radical polymerization , 2005 .

[266]  S. Perrier,et al.  Reversible Addition−Fragmentation Chain Transfer Polymerization: End Group Modification for Functionalized Polymers and Chain Transfer Agent Recovery , 2005 .

[267]  J. Yoshida,et al.  Highly versatile organostibine mediators for living radical polymerization. , 2004, Journal of the American Chemical Society.

[268]  T. Chung,et al.  A Novel “Stable” Radical Initiator Based on the Oxidation Adducts of Alkyl-9-BBN , 1996 .

[269]  A. Müller,et al.  General Kinetic Analysis and Comparison of Molecular Weight Distributions for Various Mechanisms of Activity Exchange in Living Polymerizations , 1997 .

[270]  M. Sawamoto.  Modern cationic vinyl polymerization , 1991 .

[271]  D. Haddleton,et al.  A simple method to convert atom transfer radical polymerization (ATRP) initiators into reversible addition fragmentation chain-transfer (RAFT) mediators , 2004 .

[272]  J. Fréchet,et al.  Applying key concepts from nature: transition state stabilization, pre-concentration and cooperativity effects in dendritic biomimetics , 2005 .

[273]  Malcolm B. Gillies,et al.  A DFT study of R-X bond dissociation enthalpies of relevance to the initiation process of atom transfer radical polymerization , 2003 .

[274]  O. Webster.  Living Polymerization Methods , 1991, Science.

[275]  K. Matyjaszewski,et al.  Stereoblock copolymers and tacticity control in controlled/living radical polymerization. , 2003, Journal of the American Chemical Society.

[276]  H. Maynard,et al.  One-step synthesis of low polydispersity, biotinylated poly(N-isopropylacrylamide) by ATRP. , 2005, Chemical communications.

[277]  C. Bamford.  The kinetics of vinyl polymerization by radical mechanisms , 1958 .

[278]  Yuliang Yang,et al.  Effect of Hydrogen Transfer Reaction on Kinetics of Nitroxide-Mediated Free-Radical Polymerization , 2000 .

[279]  R. B. Grubbs,et al.  Preparation of Hyperbranched and Star Polymers by a "Living", Self-Condensing Free Radical Polymerization , 1995 .

[280]  Shiping Zhu,et al.  Packed column reactor for continuous atom transfer radical polymerization: Methyl methacrylate polymerization using silica gel supported catalyst , 2000 .

[281]  P. Dubois,et al.  Controlled Radical Polymerization of Methacrylic Monomers in the Presence of a Bis(ortho-chelated) Arylnickel(II) Complex and Different Activated Alkyl Halides , 1996 .

[282]  D. Bertin,et al.  Lack of Chain Length Effect on the Rate of Homolysis of Polystyryl-SG1 Alkoxyamines , 2002 .

[283]  K. Matyjaszewski,et al.  Nanostructured carbon arrays from block copolymers of polyacrylonitrile. , 2002, Journal of the American Chemical Society.

[284]  Y. Gnanou,et al.  Kinetics and Mechanism of Controlled Free-Radical Polymerization of Styrene and n-Butyl Acrylate in the Presence of an Acyclic β-Phosphonylated Nitroxide† , 2000 .

[285]  M. Sawamoto,et al.  Living Radical Polymerization of Methyl Methacrylate with Ruthenium Complex: Formation of Polymers with Controlled Molecular Weights and Very Narrow Distributions1 , 1996 .

[286]  M. Coote,et al.  Computer-Aided Design of a Destabilized RAFT Adduct Radical: Toward Improved RAFT Agents for Styrene-block-Vinyl Acetate Copolymers , 2005 .

[287]  Krzysztof Matyjaszewski,et al.  Reversible redox cleavage/coupling of polystyrene with disulfide or thiol groups prepared by atom transfer radical polymerization , 2002 .

[288]  Y. Okamoto,et al.  Iron‐catalyzed radical polymerization of acrylamides in the presence of Lewis acid for simultaneous control of molecular weight and tacticity , 2006 .

[289]  N. Kawahara,et al.  Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization , 2003 .

[290]  K. Matyjaszewski,et al.  Nuclear magnetic resonance monitoring of chain‐end functionality in the atom transfer radical polymerization of styrene , 2005 .

[291]  K. A. Davis,et al.  Kinetic investigation of the atom transfer radical polymerization of methyl acrylate , 1999 .

[292]  Navid B. Saleh,et al.  Oil-in-water emulsions stabilized by highly charged polyelectrolyte-grafted silica nanoparticles. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[293]  Bruno Dufour,et al.  Adsorbed triblock copolymers deliver reactive iron nanoparticles to the oil/water interface. , 2005, Nano letters.

[294]  K. Matyjaszewski,et al.  Atom Transfer Radical Polymerization in Microemulsion , 2005 .

[295]  M. Sawamoto,et al.  Metal-catalyzed living radical polymerization. , 2001, Chemical reviews.

[296]  S. Słomkowski,et al.  Cationic ring-opening polymerization of heterocyclic monomers , 1980 .

[297]  K. Matyjaszewski,et al.  Effect of [Pyridylmethanimine]/[CuI] Ratio, Ligand, Solvent and Temperature on the Activation Rate Constants in Atom Transfer Radical Polymerization , 2005 .

[298]  K. Matyjaszewski,et al.  Atom transfer radical polymerization of styrene in toluene/water mixtures , 2002 .

[299]  K. A. Davis,et al.  Statistical, Gradient, Block and Graft Copolymers by Controlled/Living Radical Polymerizations , 2002 .

[300]  K. Matyjaszewski,et al.  Synthesis of Polymer Brushes Using Atom Transfer Radical Polymerization , 2003 .

[301]  K. Matyjaszewski,et al.  Synthesis of uniform protein-polymer conjugates. , 2005, Biomacromolecules.

[302]  H. Maynard,et al.  Streptavidin as a macroinitiator for polymerization: in situ protein-polymer conjugate formation. , 2005, Journal of the American Chemical Society.

[303]  R. Jerome,et al.  Synthesis of End-Functional Poly(vinyl acetate) by Cobalt-Mediated Radical Polymerization , 2005 .

[304]  K. Matyjaszewski,et al.  Synthesis of well-defined alternating copolymers by controlled/living radical polymerization in the presence of Lewis acids , 2003 .

[305]  Baiquan Wang,et al.  Controlled/“Living” Radical Polymerization of MMA Catalyzed by Cobaltocene , 2003 .

[306]  Krzysztof Matyjaszewski,et al.  Preparation of homopolymers and block copolymers in miniemulsion by ATRP using activators generated by electron transfer (AGET). , 2005, Journal of the American Chemical Society.

[307]  K. Matyjaszewski,et al.  Highly Efficient “Click” Functionalization of Poly(3-azidopropyl methacrylate) Prepared by ATRP , 2005 .

[308]  Yutaka Kobayashi,et al.  A Systematic Study on Activation Processes in Organotellurium-Mediated Living Radical Polymerizations of Styrene, Methyl Methacrylate, Methyl Acrylate, and Vinyl Acetate , 2006 .

[309]  M. Szwarc.  Ions and Ion Pairs in Organic Reactions , 1974 .

[310]  K. Matyjaszewski,et al.  Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of 2-hydroxyethyl acrylate , 1998 .

[311]  Philipp Vana,et al.  Mechanism of Dithiobenzoate‐Mediated RAFT Polymerization: A Missing Reaction Step , 2006 .

[312]  Didier Benoit,et al.  Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations , 1999 .

[313]  David J. Williams,et al.  Five-coordinate iron(II) complexes bearing tridentate nitrogen donor ligands as catalysts for atom transfer radical polymerisation , 2004 .

[314]  Shiping Zhu,et al.  ESR Study on Diffusion-Controlled Atom Transfer Radical Polymerization of Methyl Methacrylate and Ethylene Glycol Dimethacrylate , 2002 .

[315]  K. Matyjaszewski,et al.  Preparation of Hyperbranched Polyacrylates by Atom Transfer Radical Polymerization. 3. Effect of Reaction Conditions on the Self-Condensing Vinyl Polymerization of 2-((2-Bromopropionyl)oxy)ethyl Acrylate , 1997 .

[316]  Graeme Moad,et al.  Living Radical Polymerization by the RAFT Process , 2005 .

[317]  K. Matyjaszewski,et al.  Emulsion Polymerization of n-Butyl Methacrylate by Reverse Atom Transfer Radical Polymerization , 1999 .

[318]  U. Jahn.  Highly Efficient Generation of Radicals from Ester Enolates by the Ferrocenium Ion. Application to Selective alpha-Oxygenation and Dimerization Reactions of Esters. , 1998, The Journal of organic chemistry.

[319]  M. Szwarc.  Remarks on the Calculating Rates of Some Radical Reactions , 1951 .

[320]  K. Matyjaszewski,et al.  Step-Growth Polymers as Macroinitators for ``Living'' Radical Polymerization: Synthesis of ABA Block Copolymers , 1997 .

[321]  G. Moad,et al.  Living Radical Polymerization , 2005 .

[322]  D. Charmot,et al.  Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents , 2000 .

[323]  K. Matyjaszewski,et al.  Osmium-Mediated Radical Polymerization , 2005 .

[324]  J. Claverie,et al.  Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible. , 2001, Journal of the American Chemical Society.

[325]  K. Matyjaszewski,et al.  Synthesis of High Molecular Weight Poly(styrene-co-acrylonitrile) Copolymers with Controlled Architecture , 2006 .

[326]  Krzysztof Matyjaszewski,et al.  Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization , 1996, Science.

[327]  K. Matyjaszewski.  Lifetimes of Polystyrene Chains in Atom Transfer Radical Polymerization , 1999 .

[328]  Mathias Destarac,et al.  On the importance of xanthate substituents in the MADIX process , 2003 .

[329]  K. Matyjaszewski,et al.  Toward Structural and Mechanistic Understanding of Transition Metal-Catalyzed Atom Transfer Radical Processes , 2003 .

[330]  K. Matyjaszewski,et al.  Simple and Efficient Synthesis of Various Alkoxyamines for Stable Free Radical Polymerization , 1998 .

[331]  K. Matyjaszewski,et al.  Copper Triflate as a Catalyst in Atom Transfer Radical Polymerization of Styrene and Methyl Acrylate , 1998 .

[332]  T. Clark.  Radical addition to alkene–metal cation complexes , 1986 .

[333]  K. Matyjaszewski,et al.  General method for determination of the activation, deactivation, and initiation rate constants in transition metal-catalyzed atom transfer radical processes. , 2002, Journal of the American Chemical Society.

[334]  K. Matyjaszewski,et al.  ATRP of Methyl Methacrylate in the Presence of Ionic Liquids with Ferrous and Cuprous Anions , 2001 .

[335]  K. Müllen,et al.  Triazolinyl radicals – new additives for controlled radical polymerization , 1998 .

[336]  Krzysztof Matyjaszewski,et al.  Step-Growth “Click” Coupling of Telechelic Polymers Prepared by Atom Transfer Radical Polymerization , 2005 .

[337]  K. Matyjaszewski,et al.  An Immobilized/Soluble Hybrid Catalyst System for Atom Transfer Radical Polymerization , 2001 .

[338]  H. Fischer.  The Persistent Radical Effect: A Principle for Selective Radical Reactions and Living Radical Polymerizations , 2002 .

[339]  K. Matyjaszewski,et al.  Free-radical intermediates in atom transfer radical addition and polymerization : Study of racemization, halogen exchange, and trapping reactions , 2001 .

[340]  Y. Murata,et al.  A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition−Fragmentation Chain Transfer , 2002 .

[341]  D. Gigmes,et al.  Nitroxide-Mediated Polymerization: The Pivotal Role of the kd Value of the Initiating Alkoxyamine and the Importance of the Experimental Conditions , 2006 .

[342]  K. Matyjaszewski,et al.  Structure and Properties of Poly(butyl acrylate‐block‐sulfone‐block‐butyl acrylate) Triblock Copolymers Prepared by ATRP , 2005 .

[343]  Maud Save,et al.  Batch Emulsion Polymerization of Styrene Stabilized by a Hydrophilic Macro‐RAFT Agent , 2006 .

[344]  C. Barner‐Kowollik,et al.  Thioketone spin traps as mediating agents for free radical polymerization processes. , 2006, Chemical communications.

[345]  Craig J Hawker,et al.  Defect-free nanoporous thin films from ABC triblock copolymers. , 2006, Journal of the American Chemical Society.

[346]  K. Matyjaszewski.  Mechanistic and synthetic aspects of atom transfer radical polymerization , 1997 .

[347]  P. Lacroix-Desmazes,et al.  Reverse Iodine Transfer Polymerization (RITP) of Methyl Methacrylate , 2006 .

[348]  K. Matyjaszewski,et al.  Towards understanding monomer coordination in atom transfer radical polymerization: synthesis of [CuI(PMDETA)(π-M)][BPh4] (M = methyl acrylate, styrene, 1-octene, and methyl methacrylate) and structural studies by FT-IR and 1H NMR spectroscopy and X-ray crystallography , 2005 .

[349]  M. Szwarc.  Reactions of methyl radicals and their applications to polymer chemistry , 1955 .

[350]  M. Sawamoto,et al.  Catalytic activities of ruthenium(II) complexes in transition-metal-mediated living radical polymerization: Polymerization, model reaction, and cyclic voltammetry , 2000 .

[351]  S. Uchida,et al.  Free-Radical Polymerization of Macromonomers , 1995 .

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

[353]  D. Haddleton,et al.  3-aminopropyl silica supported living radical polymerization of methyl methacrylate : Dichlorotris(triphenylphosphine)ruthenium(II) mediated atom transfer polymerization , 1999 .

[354]  K. Matyjaszewski,et al.  Determination of Activation and Deactivation Rate Constants of Model Compounds in Atom Transfer Radical Polymerization1 , 2001 .

[355]  J. Michl,et al.  Li+-catalyzed radical polymerization of simple terminal alkenes. , 2006, Journal of the American Chemical Society.

[356]  K. Matyjaszewski,et al.  Kinetic study on the activation process in an atom transfer radical polymerization , 1998 .

[357]  D. Braun.  Initiation of free radical polymerization by thermal cleavage of carbon-carbon bonds , 1996 .

[358]  D. Haddleton,et al.  Copper(I)-Mediated Living Radical Polymerization under Fluorous Biphasic Conditions , 2000 .

[359]  K. Matyjaszewski,et al.  Kinetic modeling of the chain‐end functionality in atom transfer radical polymerization , 2002 .

[360]  K. Matyjaszewski,et al.  Development of an ab initio emulsion atom transfer radical polymerization: from microemulsion to emulsion. , 2006, Journal of the American Chemical Society.

[361]  C. Barner‐Kowollik,et al.  Consistent experimental and theoretical evidence for long-lived intermediate radicals in living free radical polymerization. , 2004, Journal of the American Chemical Society.

[362]  D. Greszta,et al.  TEMPO-mediated polymerization of styrene: Rate enhancement with dicumyl peroxide , 1997 .

[363]  K. Matyjaszewski,et al.  Highly active copper-based catalyst for atom transfer radical polymerization. , 2006, Journal of the American Chemical Society.

[364]  M. Szwarc.  Carbanions, Living Polymers and Electron Transfer Processes , 1968 .

[365]  M. Szwarc,et al.  POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS1 , 1956 .

[366]  H. Maynard,et al.  In situ preparation of protein-"smart" polymer conjugates with retention of bioactivity. , 2005, Journal of the American Chemical Society.

[367]  K. Matyjaszewski,et al.  Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization , 1999 .