Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

[1]  C. Barner‐Kowollik,et al.  Easy access to chain-length-dependent termination rate coefficients using RAFT polymerization , 2002 .

[2]  M. Monteiro,et al.  Influence of the Chemical Structure of MADIX Agents on the RAFT Polymerization of Styrene , 2003 .

[3]  C. Ladavière,et al.  Synthesis and Characterization of Poly(acrylic acid) Produced by RAFT Polymerization. Application as a Very Efficient Dispersant of CaCO3, Kaolin, and TiO2 , 2003 .

[4]  Deyue Yan,et al.  Kinetic Analysis of "Living" Polymerization Processes Exhibiting Slow Equilibria. 1. Degenerative Transfer (Direct Activity Exchange between Active and "Dormant" Species). Application to Group Transfer Polymerization , 1995 .

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

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

[7]  H. Mark,et al.  Encyclopedia of polymer science and engineering , 1985 .

[8]  C. Pan,et al.  Controlled alternating copolymerization of St with MAh in the presence of DBTTC , 2002 .

[9]  V. Percec,et al.  Metal Catalyzed Living Radical Polymerization of Acrylonitrile Initiated with Sulfonyl Chlorides , 2001 .

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

[11]  N. Ayres,et al.  Kinetics and Molecular Weight Control of the Polymerization of Acrylamide via RAFT , 2004 .

[12]  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 .

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

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

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

[16]  Stuart W. Prescott,et al.  Radical Loss in RAFT-Mediated Emulsion Polymerizations , 2005 .

[17]  I. Degani,et al.  Phase-Transfer Synthesis of Symmetrical and Unsymmetrical Dialkyl Trithiocarbonates , 1986 .

[18]  C. Pan,et al.  Dihydroxyl-terminated telechelic polymers prepared by RAFT polymerization using functional trithiocarbonate as chain transfer agent , 2004 .

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

[20]  J. Qian,et al.  Study on kinetics of controlled/living radical polymerization of acrylonitrile by RAFT technique , 2005 .

[21]  Shiping Zhu,et al.  Modeling the reversible addition–fragmentation transfer polymerization process , 2003 .

[22]  Stuart W. Prescott.  Chain-Length Dependence in Living/Controlled Free-Radical Polymerizations: Physical Manifestation and Monte Carlo Simulation of Reversible Transfer Agents , 2003 .

[23]  Bumjae Lee,et al.  Experimental Criteria for Living Polymerizations , 1992 .

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

[25]  B. Klumperman,et al.  Initialisation in RAFT-mediated polymerisation of methyl acrylate. , 2004, Chemical communications.

[26]  M. Monteiro,et al.  Seeded Emulsion Polymerization of Block Copolymer Core−Shell Nanoparticles with Controlled Particle Size and Molecular Weight Distribution Using Xanthate-Based RAFT Polymerization , 2004 .

[27]  R. Sanderson,et al.  A 1H NMR Investigation of Reversible Addition−Fragmentation Chain Transfer Polymerization Kinetics and Mechanisms. Initialization with Different Initiating and Leaving Groups , 2005 .

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

[29]  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 .

[30]  R. Sanderson,et al.  Beyond Inhibition:  A 1H NMR Investigation of the Early Kinetics of RAFT-Mediated Polymerization with the Same Initiating and Leaving Groups , 2004 .

[31]  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 .

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

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

[34]  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 .

[35]  Thomas P. Davis,et al.  RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes , 2003 .

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

[37]  L. Radom,et al.  Ab initio evidence for slow fragmentation in RAFT polymerization. , 2003, Journal of the American Chemical Society.

[38]  C. Barner‐Kowollik,et al.  Reversible addition fragmentation chain transfer polymerization of sterically hindered monomers: Toward well-defined rod/coil architectures , 2004 .

[39]  N. Dörr,et al.  Controlled Radical Polymerization of Acrylic Acid in Protic Media , 2001 .