Sequence-Controlled Multiblock Copolymers via RAFT Polymerization: Modeling and Simulations

The synthesis of high-order multiblock copolymers by one-pot sequential monomer addition RAFT polymerization is examined by use of modeling and simulations using PREDICI. The system is the previously experimentally investigated model multiblock homopolymer system comprising 10 blocks of N,Ndimethyl acrylamide with average degree of polymerization 10 for each block. The simulations show that despite 10 chain extensions to full conversion, the number of dead chains at the end of the process is only � 7%. The number fraction of dead chains is known from the number of chains generated from the initiator, and the conditions can thus be tailored with regards to the livingness required.

[1]  S. Perrier,et al.  Exploitation of the Degenerative Transfer Mechanism in RAFT Polymerization for Synthesis of Polymer of High Livingness at Full Monomer Conversion , 2014 .

[2]  Thomas Maschmeyer,et al.  Rapid and quantitative one-pot synthesis of sequence-controlled polymers by radical polymerization , 2013, Nature Communications.

[3]  D. Haddleton,et al.  High Molecular Weight Block Copolymers by Sequential Monomer Addition via Cu(0)-Mediated Living Radical Polymerization (SET-LRP): An Optimized Approach. , 2013, ACS macro letters.

[4]  R. Zuckermann,et al.  Polypeptoids: a model system to study the effect of monomer sequence on polymer properties and self-assembly , 2013 .

[5]  David R. Liu,et al.  Sequence-Controlled Polymers , 2013, Science.

[6]  J. Vandenbergh,et al.  Precision synthesis of acrylate multiblock copolymers from consecutive microreactor RAFT polymerizations , 2013 .

[7]  Ronan Mchale,et al.  Aqueous copper-mediated living polymerization: exploiting rapid disproportionation of CuBr with Me6TREN. , 2013, Journal of the American Chemical Society.

[8]  R. Wallis,et al.  Sequence-controlled multi-block glycopolymers to inhibit DC-SIGN-gp120 binding. , 2013, Angewandte Chemie.

[9]  David R. Liu,et al.  Enzyme-Free Translation of DNA into Sequence-Defined Synthetic Polymers Structurally Unrelated to Nucleic Acids , 2013, Nature chemistry.

[10]  J. Lutz,et al.  Microstructure Control: An Underestimated Parameter in Recent Polymer Design , 2013 .

[11]  W. Meiser,et al.  "Assessing the RAFT equilibrium constant via model systems: an EPR study"--response to a comment. , 2012, Macromolecular rapid communications.

[12]  C. Barner‐Kowollik,et al.  Thioketone-mediated polymerization with dithiobenzoates: proof for the existence of stable radical intermediates in RAFT polymerization. , 2012, Macromolecular rapid communications.

[13]  J. Patterson,et al.  Biomimetic radical polymerization via cooperative assembly of segregating templates. , 2012, Nature chemistry.

[14]  C. M. Bates,et al.  Multiblock Polymers: Panacea or Pandora’s Box? , 2012, Science.

[15]  C. Boyer,et al.  End‐group fidelity of copper(0)‐meditated radical polymerization at high monomer conversion: an ESI‐MS investigation , 2011 .

[16]  Makoto Ouchi,et al.  Single-chain technology using discrete synthetic macromolecules. , 2011, Nature chemistry.

[17]  C. Boyer,et al.  Synthesis of Complex Multiblock Copolymers via a Simple Iterative Cu(0)-Mediated Radical Polymerization Approach , 2011 .

[18]  M. Ouchi,et al.  Sequence-regulated radical polymerization with a metal-templated monomer: repetitive ABA sequence by double cyclopolymerization. , 2011, Angewandte Chemie.

[19]  C. Boyer,et al.  High-order multiblock copolymers via iterative Cu(0)-mediated radical polymerizations (SET-LRP): toward biological precision. , 2011, Journal of the American Chemical Society.

[20]  T. P. Davis,et al.  Retardation in RAFT Polymerization: Does Cross-Termination Occur with Short Radicals Only? , 2011 .

[21]  Mathias Destarac,et al.  On the Critical Role of RAFT Agent Design in Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization , 2011 .

[22]  S. Perrier,et al.  RAFT Polymerization under Microwave Irradiation: Toward Mechanistic Understanding , 2011 .

[23]  Yanbin Huang,et al.  Toward the synthesis of sequence-controlled vinyl copolymers. , 2011, Chemical communications.

[24]  Nina Fechler,et al.  Controlled folding of synthetic polymer chains through the formation of positionable covalent bridges , 2011, Nature Chemistry.

[25]  M. Ouchi,et al.  Designer template initiator for sequence regulated polymerization: systems design for substrate-selective metal-catalyzed radical addition and living radical polymerization. , 2011, Macromolecular rapid communications.

[26]  S. Perrier,et al.  Synthesis of silica-polymer hybrids by combination of RAFT polymerization and azide-alkyne cycloaddition ‘click’ reactions , 2010 .

[27]  Gregory T. Russell,et al.  Chain-length-dependent termination in radical polymerization: Subtle revolution in tackling a long-standing challenge , 2009 .

[28]  M. Gradzielski,et al.  Synthesis and Characterization of Amphiphilic Multiblock Copolymers: Effect of the Number of Blocks on Micellization , 2009 .

[29]  Brian S. Hawkett,et al.  RAFT polymerization kinetics: How long are the cross‐terminating oligomers? , 2009 .

[30]  Brian S. Hawkett,et al.  Obtaining kinetic information from the chain-length distribution of polymers produced by RAFT. , 2009, The journal of physical chemistry. B.

[31]  Michael Wulkow,et al.  Computer Aided Modeling of Polymer Reaction Engineering—The Status of Predici, I‐Simulation , 2008 .

[32]  Christopher Barner-Kowollik,et al.  The future of reversible addition fragmentation chain transfer polymerization , 2008 .

[33]  P. Zetterlund,et al.  Controlled/living radical polymerization in dispersed systems. , 2008, Chemical reviews.

[34]  Brian S. Hawkett,et al.  RAFT Polymerization Kinetics : Combination of Apparently Conflicting Models , 2008 .

[35]  G. Moad,et al.  Living Radical Polymerization by the RAFT Process - A Second Update , 2006 .

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

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

[38]  C. Barner‐Kowollik,et al.  Chain length dependent termination in butyl acrylate free-radical polymerization studied via stationary and pulsed laser initiated RAFT polymerization , 2005 .

[39]  J. Storsberg,et al.  Stimuli responsive amphiphilic block copolymers for aqueous media synthesised via reversible addition fragmentation chain transfer polymerisation (RAFT) , 2005 .

[40]  Gregory T. Russell,et al.  General Solution to the Band-Broadening Problem in Polymer Molecular Weight Distributions* , 2005 .

[41]  Shane A. Seabrook,et al.  Pulsed laser polymerization study of the propagation kinetics of acrylamide in water , 2005 .

[42]  P. Zetterlund,et al.  Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate , 2004 .

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

[44]  C. Barner‐Kowollik,et al.  Implementing the reversible addition–fragmentation chain transfer process in PREDICI , 2004 .

[45]  Gregory T. Russell,et al.  Termination in Dilute‐Solution Free‐Radical Polymerization: A Composite Model , 2003 .

[46]  M. Monteiro,et al.  Pulsed-laser polymerization (PLP) of N-isopropyl acrylamide (NIPAM) in water: a qualitative study , 2000 .

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

[48]  C. Boyer,et al.  Synthesis of multi-block copolymer stars using a simple iterative Cu(0)-mediated radical polymerization technique , 2012 .

[49]  Krzysztof Matyjaszewski,et al.  Controlled/living radical polymerization: Features, developments, and perspectives , 2007 .