PMDETA as an efficient catalyst for bulk reversible complexation mediated polymerization (RCMP) in the absence of additional metal salts and deoxygenation

Reversible-deactivation radical polymerization (RDRP) represents one of the most rapid developments in functional polymer synthesis with a well-defined structure and architecture. In this work, N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) without any metal salts was used as an efficient catalyst for reversible complexation mediated polymerization (RCMP) of methyl methacrylate (MMA) in bulk. The polymerization showed typical features of RDRP. Importantly, well-defined polymers with controllable molecular weights and narrow molecular weight distributions were obtained in the absence of any additional deoxygenation. PMDETA as a catalyst for RCMP not only could simplify the polymerization process and post-treatment but also would be applicable as one of the most robust and powerful techniques for polymer synthesis.

[1]  A. Goto,et al.  Theoretical and Experimental Studies on Elementary Reactions in Living Radical Polymerization via Organic Amine Catalysis , 2016 .

[2]  Dashu Chen,et al.  Visible-light-induced controlled radical polymerization of methacrylates mediated by a pillared-layer metal–organic framework , 2016 .

[3]  Woong Young So,et al.  Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies. , 2016, Journal of the American Chemical Society.

[4]  Zhenping Cheng,et al.  Facile iron(III)-mediated ATRP of MMA with phosphorus-containing ligands in the absence of any additional initiators , 2015 .

[5]  Minghua Wang,et al.  Triphenylphosphine as reducing agent for copper(II)-catalyzed AGET ATRP , 2015, Chinese Journal of Polymer Science.

[6]  Minghua Wang,et al.  Reversible chain transfer catalyzed polymerization (RTCP) in nitrogen-based solvents without additional catalysts , 2015 .

[7]  K. Matyjaszewski,et al.  Photoinduced Metal-Free Atom Transfer Radical Polymerization of Acrylonitrile. , 2015, ACS macro letters.

[8]  C. Hawker,et al.  Metal-free atom transfer radical polymerization. , 2014, Journal of the American Chemical Society.

[9]  Chun-peng Wang,et al.  Integration of renewable cellulose and rosin towards sustainable copolymers by “grafting from” ATRP , 2014 .

[10]  K. Matyjaszewski,et al.  Towards sustainable polymer chemistry with homogeneous metal-based catalysts , 2014 .

[11]  H. Kaji,et al.  Living Radical Polymerization via Organic Superbase Catalysis , 2014 .

[12]  H. Kaji,et al.  Reversible generation of a carbon-centered radical from alkyl iodide using organic salts and their application as organic catalysts in living radical polymerization. , 2013, Journal of the American Chemical Society.

[13]  Zhenping Cheng,et al.  Developing a Synthetic Approach with Thermoregulated Phase-Transfer Catalysis: Facile Access to Metal-Mediated Living Radical Polymerization of Methyl Methacrylate in Aqueous/Organic Biphasic System , 2013 .

[14]  S. Clerc,et al.  CONTROLLED RADICAL POLYMERIZATION OF 1,1,2,2-TETRAHYDROPERFLUORODECYL ACRYLATE BY REVERSE IODINE TRANSFER POLYMERIZATION (RITP) , 2013 .

[15]  Zhenping Cheng,et al.  Activators generated by electron transfer for atom transfer radical polymerization: recent advances in catalyst and polymer chemistry , 2012 .

[16]  Wantai Yang,et al.  Cycloketyl radical mediated living polymerization , 2012 .

[17]  H. Minami,et al.  Preparation of block copolymer particles by two-step, reversible chain transfer catalyzed polymerization (RTCP) with nitrogen catalyst in miniemulsion systems , 2012 .

[18]  H. Minami,et al.  Iodine Transfer Polymerization (ITP with CHI3) and Reversible Chain Transfer Catalyzed Polymerization (RTCP with Nitrogen Catalyst) of Methyl Methacrylate in Aqueous Microsuspension Systems: Comparison with Bulk System , 2012 .

[19]  T. Fukuda,et al.  Reversible Complexation Mediated Living Radical Polymerization (RCMP) Using Organic Catalysts , 2011 .

[20]  Lifen Zhang,et al.  Alumina additives for fast iron-mediated AGET ATRP of MMA using onium salt as ligand , 2011 .

[21]  Zhenping Cheng,et al.  Rate‐enhanced ATRP in the presence of catalytic amounts of base: An example of iron‐mediated AGET ATRP of MMA , 2011 .

[22]  Y. Tu,et al.  Iron-Mediated AGET ATRP of Styrene in the Presence of Catalytic Amounts of Base , 2010 .

[23]  H. Minami,et al.  Reversible Chain Transfer Catalyzed Polymerization (RTCP) of Methyl Methacrylate with Nitrogen Catalyst in an Aqueous Microsuspension System , 2010 .

[24]  T. Fukuda,et al.  Phenols and Carbon Compounds as Efficient Organic Catalysts for Reversible Chain Transfer Catalyzed Living Radical Polymerization (RTCP) , 2010 .

[25]  Rachel K. O'Reilly,et al.  End group removal and modification of RAFT polymers , 2010 .

[26]  G. Moad,et al.  Terminology for reversible-deactivation radical polymerization previously called "controlled" radical or "living" radical polymerization (IUPAC Recommendations 2010) , 2009 .

[27]  Huayu Qiu,et al.  AGET ATRP of methyl methacrylate with poly(ethylene glycol) (PEG) as solvent and TMEDA as both ligand and reducing agent , 2009 .

[28]  Krzysztof Matyjaszewski,et al.  Nanostructured functional materials prepared by atom transfer radical polymerization , 2009, Nature Chemistry.

[29]  Zhenping Cheng,et al.  Iron(III)‐mediated AGET ATRP of styrene using tris(3,6‐dioxaheptyl)amine as a ligand , 2009 .

[30]  K. Matyjaszewski,et al.  ARGET ATRP of methyl methacrylate in the presence of nitrogen‐based ligands as reducing agents , 2009 .

[31]  T. Fukuda,et al.  REVERSIBLE CHAIN TRANSFER CATALYZED POLYMERIZATION (RTCP): A NEW CLASS OF LIVING RADICAL POLYMERIZATION , 2008 .

[32]  T. Fukuda,et al.  LIVING RADICAL POLYMERIZATION WITH NITROGEN CATALYST: REVERSIBLE CHAIN TRANSFER CATALYZED POLYMERIZATION WITH N-IODOSUCCINIMIDE , 2008 .

[33]  K. Matyjaszewski,et al.  Atom transfer radical addition and polymerization reactions catalyzed by ppm amounts of copper complexes. , 2008, Chemical Society reviews.

[34]  C. Detrembleur,et al.  In-situ nitroxide-mediated radical polymerization (NMP) processes: their understanding and optimization. , 2008, Chemical reviews.

[35]  K. Matyjaszewski,et al.  "Green" atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials. , 2007, Chemical reviews.

[36]  P. Lacroix-Desmazes,et al.  Use of iodocompounds in radical polymerization. , 2006, Chemical reviews.

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

[38]  Shiping Zhu,et al.  Thermal‐initiated reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in the presence of oxygen , 2006 .

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

[40]  Graeme Moad,et al.  Living radical polymerization by the RAFT process , 2005 .

[41]  Bernard Boutevin,et al.  Reverse Iodine Transfer Polymerization of Methyl Acrylate and n-Butyl Acrylate , 2005 .

[42]  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 .

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

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

[45]  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 .

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

[47]  K. Matyjaszewski,et al.  Controlled Living Radical Polymerization - Halogen Atom-Transfer Radical Polymerization Promoted by a Cu(I)Cu(II) Redox Process , 1995 .

[48]  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 .

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

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

[51]  Zhenping Cheng,et al.  An atom transfer radical polymerization system: catalyzed by an iron catalyst in PEG-400 , 2015 .

[52]  H. Kaji,et al.  Reversible Complexation Mediated Polymerization (RCMP) of Methyl Methacrylate , 2012 .

[53]  P. Lacroix-Desmazes,et al.  Controlled Radical Polymerization of Styrene by Reverse Iodine Transfer Polymerization (RITP) in Miniemulsion: Use of Hydrogen Peroxide as Oxidant , 2007 .