Kinetic insight into electrochemically mediated ATRP gained through modeling

A detailed kinetic model was constructed using the method of moments to elucidate the electrochemically mediated atom transfer radical polymerization (eATRP). Combined with electrochemical theory, the reducing rate coefficient relevant to the overpotential in eATRP was coupled into the kinetic model. The rate coefficients for eATRP equilibrium and the reducing rate coefficient were fitted to match the experimental data. The effects of catalyst loading, overpotential, and application of programmable electrolysis on the eATRP behavior were investigated based on the tested kinetic model. Results showed that the apparent polymerization rate exhibited a square root dependence on catalyst loading. In addition, a more negative potential accelerated the polymerization rate before the mass transport limitation was reached. This phenomenon indicated that the polymerization rate could be artificially controlled by the designed program (i.e., stepwise and intermittent electrolysis programs). What is more, the normal ATRP, photo-ATRP, and eATRP were compared to obtain a deeper understanding of these ATRP systems. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4347–4357, 2015

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

[2]  M. Cunningham,et al.  ARGET ATRP of BMA and BA: Exploring Limitations at Low Copper Levels , 2012 .

[3]  Zheng‐Hong Luo,et al.  Copper(0)-Mediated Reversible-Deactivation Radical Polymerization: Kinetics Insight and Experimental Study , 2014 .

[4]  José M. Asua,et al.  Modeling of Seeded Semibatch Emulsion Polymerization of n-BA , 2001 .

[5]  Krzysztof Matyjaszewski,et al.  Kinetic Modeling of ICAR ATRP , 2012 .

[6]  Zheng-Hong Luo,et al.  Theoretical Modeling Coupled with Experimental Study on the Preparation and Characterization Comparison of Fluorinated Copolymers: Effect of Chain Structure on Copolymer Properties , 2013 .

[7]  Dagmar R. D’hooge,et al.  Atom Transfer Radical Polymerization of Isobornyl Acrylate: A Kinetic Modeling Study , 2010 .

[8]  A. N. Nikitin,et al.  Determination of Intramolecular Chain Transfer and Midchain Radical Propagation Rate Coefficients for Butyl Acrylate by Pulsed Laser Polymerization , 2007 .

[9]  Krzysztof Matyjaszewski,et al.  How are radicals (re)generated in photochemical ATRP? , 2014, Journal of the American Chemical Society.

[10]  Tao Chen,et al.  ATRP with a light switch: photoinduced ATRP using a household fluorescent lamp , 2014 .

[11]  Y. Yagcı,et al.  Studies on Photoinduced ATRP in the Presence of Photoinitiator , 2011 .

[12]  Dagmar R. D’hooge,et al.  Origin of the Difference between Branching in Acrylates Polymerization under Controlled and Free Radical Conditions: A Computational Study of Competitive Processes , 2011 .

[13]  Mathias Destarac,et al.  Controlled Radical Polymerization: Industrial Stakes, Obstacles and Achievements , 2010 .

[14]  Krzysztof Matyjaszewski,et al.  ARGET ATRP of 2-(Dimethylamino)ethyl Methacrylate as an Intrinsic Reducing Agent , 2008 .

[15]  Krzysztof Matyjaszewski,et al.  Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. Kinetic Simulation , 2013 .

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

[17]  Guy Marin,et al.  The Long and the Short of Radical Polymerization , 2015 .

[18]  Shiping Zhu,et al.  Modeling of molecular weight development in atom transfer radical polymerization , 1999 .

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

[20]  Guy Marin,et al.  ARGET ATRP of Butyl Methacrylate: Utilizing Kinetic Modeling To Understand Experimental Trends , 2013 .

[21]  H. Fischer,et al.  Rate constants for some prototype radical reactions in liquids by kinetic electron spin resonance , 1987 .

[22]  Krzysztof Matyjaszewski,et al.  Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives , 2012 .

[23]  D. Gigmes,et al.  3.10 - Nitroxide-Mediated Polymerization , 2012 .

[24]  K. Matyjaszewski,et al.  Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. Comproportionation–Disproportionation Equilibria and Kinetics , 2013 .

[25]  K. Matyjaszewski,et al.  Kinetic Modeling of Normal ATRP, Normal ATRP with [CuII]0, Reverse ATRP and SR&NI ATRP , 2008 .

[26]  K. Matyjaszewski,et al.  Solvent Effects on the Activation Rate Constant in Atom Transfer Radical Polymerization , 2013 .

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

[28]  Shiping Zhu,et al.  Model development for semicontinuous production of ethylene and norbornene copolymers having uniform composition , 2009 .

[29]  K. Matyjaszewski,et al.  ICAR ATRP with ppm Cu Catalyst in Water , 2012 .

[30]  Zheng-Hong Luo,et al.  An old kinetic method for a new polymerization mechanism: Toward photochemically mediated ATRP , 2015 .

[31]  José M. Asua,et al.  Critically Evaluated Rate Coefficients for Free‐Radical Polymerization, 5, , 2004 .

[32]  G. Moad,et al.  Living Radical Polymerization by the RAFT Process — A Third Update , 2013 .

[33]  Dagmar R. D’hooge,et al.  Methodology for Kinetic Modeling of Atom Transfer Radical Polymerization , 2009 .

[34]  K. Matyjaszewski,et al.  Investigation of Electrochemically Mediated Atom Transfer Radical Polymerization , 2013 .

[35]  S. Jurga,et al.  Star Synthesis Using Macroinitiators via Electrochemically Mediated Atom Transfer Radical Polymerization , 2013 .

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

[37]  W. Huck,et al.  Electrochemically induced surface-initiated atom-transfer radical polymerization. , 2012, Angewandte Chemie.

[38]  Yin‐Ning Zhou,et al.  Insight into the ATRP rate controlling ability of initiator structure: Micromolecular, macromolecular, and immobilized initiators , 2014 .

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

[40]  Bo-Geng Li,et al.  Kinetics and Modeling of Solution ARGET ATRP of Styrene, Butyl Acrylate, and Methyl Methacrylate , 2011 .

[41]  Shiping Zhu,et al.  Control of gradient copolymer composition in ATRP using semibatch feeding policy , 2007 .

[42]  K. Matyjaszewski,et al.  Electrochemically Mediated Atom Transfer Radical Polymerization , 2011, Science.

[43]  Dagmar R. D’hooge,et al.  The Crucial Role of Diffusional Limitations in Controlled Radical Polymerization , 2013 .

[44]  Dagmar R. D’hooge,et al.  Computer-Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n-Butyl Acrylate , 2013 .

[45]  K. Matyjaszewski,et al.  Controlled aqueous atom transfer radical polymerization with electrochemical generation of the active catalyst. , 2011, Angewandte Chemie.

[46]  K. Matyjaszewski,et al.  Simplified electrochemically mediated atom transfer radical polymerization using a sacrificial anode. , 2015, Angewandte Chemie.

[47]  R. Hutchinson,et al.  Secondary Reactions in the High-Temperature Free Radical Polymerization of Butyl Acrylate , 2004 .

[48]  Y. Yagcı,et al.  Visible Light‐Induced Atom Transfer Radical Polymerization , 2012 .

[49]  Shiping Zhu,et al.  Synthesis of ethylene/1‐octene copolymers with controlled block structures by semibatch living copolymerization , 2013 .

[50]  Shiping Zhu,et al.  Modeling the Influence of Diffusion-Controlled Reactions and Residual Termination and Deactivation on the Rate and Control of Bulk ATRP at High Conversions , 2015 .

[51]  K. Matyjaszewski,et al.  Improving the “Livingness” of ATRP by Reducing Cu Catalyst Concentration , 2013 .

[52]  K. Matyjaszewski,et al.  Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. A Critical Assessment of the SARA ATRP and SET-LRP Mechanisms , 2013 .

[53]  Dagmar R. D’hooge,et al.  Controlled synthesis of poly[(butyl methacrylate)-co-(butyl acrylate)] via activator regenerated by electron transfer atom transfer radical polymerization: insights and improvement , 2014 .

[54]  Shiping Zhu,et al.  Effects of diffusion‐controlled reactions on atom‐transfer radical polymerization , 2002 .

[55]  B. Li,et al.  Electrochemically mediated atom transfer radical polymerization on nonconducting substrates: controlled brush growth through catalyst diffusion. , 2013, Journal of the American Chemical Society.

[56]  K. Matyjaszewski,et al.  Thermodynamic Components of the Atom Transfer Radical Polymerization Equilibrium: Quantifying Solvent Effects , 2009 .

[57]  C. Barner‐Kowollik,et al.  Investigating cu(0)-mediated polymerizations: New kinetic insights based on a comparison of kinetic modeling with experimental data , 2013 .

[58]  K. Matyjaszewski,et al.  Successful Chain Extension of Polyacrylate and Polystyrene Macroinitiators with Methacrylates in an ARGET and ICAR ATRP , 2007 .