Universal Kinetic Modeling of RAFT Polymerization using Moment Equations

Authors: Mehdi Salami-Kalajahi, Pejman Ganjeh-Anzabi, Vahid Haddadi-Asl, Mohammad Najafi

Abstract:

In the following text, we show that by introducing universal kinetic scheme, the origin of rate retardation and inhibition period which observed in dithiobenzoate-mediated RAFT polymerization can be described properly. We develop our model by utilizing the method of moments, then we apply our model to different monomer/RAFT agent systems, both homo- and copolymerization. The modeling results are in an excellent agreement with experiments and imply the validity of universal kinetic scheme, not only for dithiobenzoate-mediated systems, but also for different types of monomer/RAFT agent ones.

Keywords: RAFT Polymerization, Mechanism, Kinetics, Moment Equations, Modeling.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1062594

References:

[1] J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, S. H. Thang, "Living Free-Radical Polymerization by Reversible Addition- Fragmentation Chain Transfer: The RAFT Process", Macromolecules, vol. 31, pp. 5559-5562, 1998.
[2] D. G. Hawthorne, G. Moad, E. Rizzardo, S. H. Thang, "Living Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT): Direct ESR Observation of Intermediate Radicals", Macromolecules, vol. 32, pp. 5457-5459, 1999.
[3] C. M. Schilli, M. Zhang, E. Rizzardo, S. H. Thang, Y. K. Chong, K. Edwards, G. Karlsson, A. H. E. Mueller, "A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N isopropylacrylamide)-block-poly(acrylic acid)", Macromolecules, vol. 37, pp. 7861-7866, 2004.
[4] Y. K. Chong, T. P. T. Le, G. Moad, E. Rizzardo, S. H. Thang, "A More Versatile Route to Block Copolymers and Other Polymers of Complex Architecture by Living Radical Polymerization: The RAFT Process", Macromolecules, vol. 32, pp. 2071-2074, 1999.
[5] H. De Brouwer, M. A. J. Schellekens, B. Klumperman, M. J. Monteiro, A. L. German, "Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition-fragmentation chain-transfer (RAFT) polymerization", J. Polym Sci Part A: Polym Chem., vol. 38, pp. 3596- 3603, 2000.
[6] X. Sun, Y. Luo, R. Wang, B. Li, B. Liu, S. Zhu, "Programmed Synthesis of Copolymer with Controlled Chain Composition Distribution via Semibatch RAFT Copolymerization", Macromolecules, vol. 40, pp. 849- 859, 2007.
[7] R. T. A. Mayadunne, J. Jeffery, G. Moad, E. Rizzardo, "Living Free Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT Polymerization): Approaches to Star Polymers", Macromolecules, vol. 36, pp. 1505-1513, 2003.
[8] S. Perrier, P. Takolpuckdee, "Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization", J. Polym. Sci., Part A: Polym. Chem., vol. 43, pp. 5347-5393, 2005.
[9] G. Moad, R. T. A. Mayadunne, E. Rizzardo, M. Skidmore, S. H. Thang, "Synthesis of novel architectures by radical polymerization with reversible addition fragmentation chain transfer (RAFT polymerization)", Macromol. Symp., vol. 192, 1-12, 2003.
[10] L. Barner, C. Barner-Kowollik, T. P. Davis, M. H. Stenzel, "Complex Molecular Architecture Polymers via RAFT", Aust. J. Chem., vol. 57, pp. 19-24, 2004.
[11] C. Barner-Kowollik, T. P. Davis, M. H. Stenzel, "Synthesis of star polymers via RAFT polymerization: What is possible?", Aust. J. Chem., vol. 59, pp. 719-727, 2006.
[12] B. Liu, A. Kazlauciunas, J. T. Guthrie, S. Perrier, "One-Pot Hyperbranched Polymer Synthesis Mediated by Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization", Macromolecules, vol. 38, pp. 2131-2136, 2005.
[13] C. Barner-Kowollik, M. Buback, B. Charleux, M. L. Coote, M. Drache, T. Fukuda, A. Goto, B. Klumperman, A. B. Lowe, J. B. McLeary, G. Moad, M. J. Monteiro, R. D. Sanderson, M. P. Tonge, P. Vana, "Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation", J. Polym. Sci., Part A: Polym. Chem., vol. 44, pp. 5809-5831, 2006.
[14] M. J. Monteiro, "Design strategies for controlling the molecular weight and rate using reversible addition-fragmentation chain transfer mediated living radical polymerization", J. Polym. Sci., Part A: Polym. Chem., vol. 43, pp. 3189-3204, 2005.
[15] C. Barner-Kowollik, J. F. Quinn, D. R. Morsley, T. P. Davis, "Modeling the reversible addition-fragmentation chain transfer process in cumyl dithiobenzoate-mediated styrene homopolymerizations: Assessing rate coefficients for the addition-fragmentation equilibrium", J. Polym. Sci., Part A: Polym. Chem., vol. 39, pp. 1353-1365, 2001.
[16] A. Feldermann, M. L. Coote, M. H. Stenzel, T. P. Davis, C. Barner- Kowollik, "Consistent Experimental and Theoretical Evidence for Long- Lived Intermediate Radicals in Living Free Radical Polymerization", J. Am. Chem. Soc., vol. 126, pp. 15915-19923, 2004.
[17] M. J. Monteiro, H. de Brouwer, "Intermediate Radical Termination as the Mechanism for Retardation in Reversible Addition−Fragmentation Chain Transfer Polymerization", Macromolecules, vol. 34, pp. 349-352, 2001.
[18] M. Drache, G. Schmidt-Naake, M. Buback, P. Vana, "Modeling RAFT polymerization kinetics via Monte Carlo methods: cumyl dithiobenzoate mediated methyl acrylate polymerization", Polymer, vol. 46, pp. 8483- 8493, 2005.
[19] M. Buback, P. Vana, "Mechanism of Dithiobenzoate-Mediated RAFT Polymerization: A Missing Reaction Step", Macromol. Rapid Commun., vol. 27, pp. 1299-1305, 2006.
[20] M. Buback, O. Janssen, R. Oswald, S. Schmatz, P. Vana, "A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization", Macromol. Symp., vol. 248, pp. 158-167, 2007.
[21] J. Pallares, G. Jaramillo-Soto, C. Flores-Catano, E. Vivaldo Lima, L. M. F. Lona, A. Penlidis, "A Comparison of Reaction Mechanisms for Reversible Addition-Fragmentation Chain Transfer Polymerization Using Modeling Tools", J. Macromol. Sci., Pure Appl. Chem., vol. 43, pp. 1293-1322, 2006.
[22] S. W. Prescott, "Chain-Length Dependence in Living/Controlled Free- Radical Polymerizations: Physical Manifestation and Monte Carlo Simulation of Reversible Transfer Agents", Macromolecules, vol. 36, pp. 9608-9621, 2003.
[23] S. W. Prescott, M. J. Ballard, E. Rizzardo, R. G. Gilbert, "Rate Optimization in Controlled Radical Emulsion Polymerization Using RAFT", Macromol. Theory Simul., vol. 15, pp. 70-86, 2006.
[24] A. R. Wang, S. Zhu, "Modeling the reversible addition-fragmentation transfer polymerization process", J. Polym. Sci., Part A: Polym. Chem., vol. 41, pp. 1553-1566, 2003.
[25] A. R. Wang, S. Zhu, "Effects of Diffusion-Controlled Radical Reactions on RAFT Polymerization", Macromol. Theory Simul., vol. 12, pp. 196- 208, 2003.
[26] M. L. Coote, L. Radom, "Ab Initio Evidence for Slow Fragmentation in RAFT Polymerization", J. Am. Chem. Soc., vol. 125 , pp. 1490-1491, 2003.
[27] M. L. Coote, E. H. Krenske, E. I. Izgorodina, "Computational Studies of RAFT Polymerization-Mechanistic Insights and Practical Applications", Macromol. Rapid Commun., vol. 27, pp. 473-497, 2006.
[28] M. L. Coote, E. I. Izgorodina, E. H. Krenske, M. Busch, C. Barner- Kowollik, "Quantum Chemical Mapping of Initialization Processes in RAFT Polymerization", Macromol. Rapid Commun., vol. 27, pp. 1015- 1022, 2006.
[29] E. I. Izgorodina, M. L. Coote, "Accurate ab initio prediction of propagation rate coefficients in free-radical polymerization: Acrylonitrile and vinyl chloride", Chem. Phys., vol. 324, 96-110, 2006.
[30] M. L. Coote, C. Barner-Kowollik, "Ab Initio Kinetic Modelling: A Paradigm Shift in Kinetic Data Analysis", Aust. J. Chem., vol. 59, pp. 712-718, 2006.
[31] D. H. Nguyen, P. Vana, "On the Mechanism of Radical Polymerization of Methyl Methacrylate using Dithiobenzoic Acid as Mediator", Aust. J. Chem., vol. 59, pp. 549-559, 2006.
[32] Y. Kwak, A. Goto, Y. Tsujii, Y. Murata, K. Komatsu, T. Fukuda, "A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition−Fragmentation Chain Transfer", Macromolecules, vol. 35, pp. 3026-3029, 2002.
[33] A. Goto, K. Sato, Y. Tsujii, T. Fukuda, G. Moad, E. Rizzardo, S. H. Thang, "Mechanism and Kinetics of RAFT-Based Living Radical Polymerizations of Styrene and Methyl Methacrylate", Macromolecules, vol. 34, pp. 402-408, 2001.
[34] S. Perrier, C. Barner-Kowollik, J. F. Quinn, P. Vana, T. P. Davis, "Origin of Inhibition Effects in the Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate", Macromolecules, vol. 35, pp. 8300-8306, 2002.
[35] C. Barner-Kowollik, M. L. Coote, T. P. Davis, L. Radom, P. Vana, "The reversible addition-fragmentation chain transfer process and the strength and limitations of modeling: Comment on the magnitude of the fragmentation rate coefficient ", J. Polym. Sci., Part A: Polym. Chem., vol. 41, pp. 2828-2832, 2003.
[36] A. R. Wang, S. Zhu, Y. Kwak, A. Goto, T. Fukuda, M. J. Monteiro, "A difference of six orders of magnitude: A reply to the magnitude of the fragmentation rate coefficient ", J. Polym. Sci., Part A: Polym. Chem., vol. 41, pp. 2833-2839, 2003.
[37] C. Barner-Kowollik, P. Vana, J. F. Quinn, T. P. Davis, "Long-lived intermediates in reversible addition-fragmentation chain-transfer (RAFT) polymerization generated by ╬│ radiation", J. Polym. Sci., Part A: Polym. Chem., vol. 40, pp. 1058-1063, 2002.
[38] G. Moad, J. Chiefari, Y. K. Chong, J. Krstina, R. T. A. Mayadunne, A. Postma, E. Rizzardo, S. H. Thang, "Living free radical polymerization with reversible addition - fragmentation chain transfer (the life of RAFT)", Polym. Int., vol. 49, pp. 993-1001, 2000.
[39] A. Ah Toy, P. Vana, T. P. Davis, C. Barner-Kowollik, "Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate: Detailed Structural Investigation via Coupled Size Exclusion Chromatography−Electrospray Ionization Mass Spectrometry (SEC−ESI-MS)", Macromolecules, vol. 37, pp. 744-751, 2004.
[40] P. Vana, T. P. Davis, C. Barner-Kowollik, "Kinetic Analysis of Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerizations: Conditions for Inhibition, Retardation, and Optimum Living Polymerization", Macromol. Theory Simul., vol. 11, pp. 823-835, 2002.
[41] C. Barner-Kowollik, J. F. Quinn, T. L. U. Nguyen, J. P. A. Heuts, T. P. Davis, "Kinetic Investigations of Reversible Addition Fragmentation Chain Transfer Polymerizations: Cumyl Phenyldithioacetate Mediated Homopolymerizations of Styrene and Methyl Methacrylate", Macromolecules, vol. 34, 7849-7857, 2001.
[42] P. Vana, J. F. Quinn, T. P. Davis, C. Barner-Kowollik, "Recent Advances In The Kinetics Of Reversible Addition Fragmentation Chain Transfer Polymerization", Aust. J. Chem., vol. 55, pp. 425-431, 2002.
[43] C. Barner-Kowollik, T. P. Davis, J. P. A. Heuts, M. H. Stenzel, P. Vana, M. Whittaker, "RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes", J. Polym. Sci. Part A: Polym. Chem., vol. 41, 365-375, 2003.
[44] T. P. Davis, C. Barner-Kowollik, T. L. U. Nguyen, M. H. Stenzel, J. F. Quinn, P. Vana, "Influences of the Structural Design of RAFT Agents on Living Radical Polymerization Kinetics", ACS Symp. Ser., vol. 854, pp. 551-569, 2003.
[45] Y. Kwak, A. Goto, T. Fukuda, "Rate Retardation in Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization: Further Evidence for Cross-Termination Producing 3-Arm Star Chain", Macromolecules, vol. 37, pp. 1219-1225, 2004.
[46] E. Chernikova, A. Morozov, E. Leonova, E. Garina, V. Golubev, C. Bui, B. Charleux, "Controlled Free-Radical Polymerization of n-Butyl Acrylate by Reversible Addition−Fragmentation Chain Transfer in the Presence of tert-Butyl Dithiobenzoate. A Kinetic Study", Macromolecules, vol. 37, pp. 6329-6339, 2004.
[47] F. M. Calitz, M. P. Tonge, R. D. Sanderson, "Kinetic and Electron Spin Resonance Analysis of RAFT Polymerization of Styrene", Macromolecules, vol. 36, pp. 5-8, 2003.
[48] F. M. Calitz, M. P. Tonge, R. D. Sanderson, "Electron spin resonance studies of reversible addition-fragmentation transfer polymerisation", Macromol. Symp., vol. 193, pp. 277-288, 2003.
[49] Y. Kwak, A. Goto, K. Komatsu, Y. Sugiura, T. Fukuda, "Characterization of Low-Mass Model 3-Arm Stars Produced in Reversible Addition−Fragmentation Chain Transfer (RAFT) Process", Macromolecules, vol. 37, pp. 4434-4440, 2004.
[50] T. Arita, M. Buback, O. Janssen, P. Vana, "RAFT-Polymerization of Styrene up to High Pressure: Rate Enhancement and Improved Control", Macromol. Rapid Commun., vol. 25, pp. 1376-1381, 2004.
[51] T. Arita, S. Beuermann, M. Buback, P. Vana, "RAFT Polymerization of Methyl Acrylate in Carbon Dioxide", Macromol. Mater. Eng., vol. 290, pp. 283-293, 2005.
[52] T. Arita, M. Buback, P. Vana, "Cumyl Dithiobenzoate Mediated RAFT Polymerization of Styrene at High Temperatures", Macromolecules, vol. 38, pp. 7935-7943, 2005.
[53] F. M. Calitz, J. B. McLeary, J. M. McKenzie, M. P. Tonge, B. Klumperman, R. D. Sanderson, "Evidence for Termination of Intermediate Radical Species in RAFT-Mediated Polymerization", Macromolecules, vol. 36, pp. 9687-9690, 2003.
[54] R. Venkatesh, B. B. P. Staal, B. Klumperman, M. J. Monteiro, "Characterization of 3- and 4-Arm Stars from Reactions of Poly(butyl acrylate) RAFT and ATRP Precursors", Macromolecules, vol. 37, pp. 7906-7917, 2004.
[55] A. Alberti, M. Benaglia, M. Laus, D. Macciantelli, K. Sparnacci, "Direct ESR Detection of Free Radicals in the RAFT Polymerization of Styrene", Macromolecules, vol. 36, pp. 736-740, 2003.
[56] M. P. Tonge, F. M. Calitz, R. D. Sanderson, "ESR Detection of Propagating Radical Species during RAFT-Mediated Polymerization", Macromol. Chem. Phys., vol. 207, pp. 1852-1860, 2006.
[57] E. T. A. Van Den Dungen, H. Matahwa, J. B. McLeary, R. D. Sanderson, B. Klumperman, "Initialization behavior at various target molecular weight RAFT-mediated methyl acrylate polymerizations", J. Polym. Sci., Part A: Polym. Chem., vol. 46, pp. 2500-2509, 2008.
[58] J. B. McLeary, F. M. Calitz, J. M. McKenzie, M. P. Tonge, R. D. Sanderson, B. Klumperman, "A 1H NMR Investigation of Reversible Addition−Fragmentation Chain Transfer Polymerization Kinetics and Mechanisms. Initialization with Different Initiating and Leaving Groups", Macromolecules, vol. 38, pp. 3151-3161, 2005.
[59] J. B. McLeary, F. M. Calitz, J. M. McKenzie, M. P. Tonge, R. D. Sanderson, B. Klumperman, "Beyond Inhibition: A 1H NMR Investigation of the Early Kinetics of RAFT-Mediated Polymerization with the Same Initiating and Leaving Groups", Macromolecules, vol. 37, pp. 2383-2394, 2004.
[60] J. B. McLeary, J. M. McKenzie, M. P. Tonge, R. D. Sanderson, B. Klumperman, "Initialisation in RAFT-mediated polymerisation of methyl acrylate", Chem. Commun., 1950, 2004.
[61] H. Tobita, F. Yanase, "Monte Carlo Simulation of Controlled/Living Radical Polymerization in Emulsified Systems", Macromol. Theory Simul., vol. 16, pp. 476-488, 2007.
[62] H. Chaffey-Millar, D. Stewart, M. M. T. Chakravarty, G. Keller, C. Barner-Kowollik, "A Parallelised High Performance Monte Carlo Simulation Approach for Complex Polymerisation Kinetics", Macromol. Theory Simul., vol. 16, pp. 575-592, 2007.
[63] D. Konkolewicz, B. S. Hawkett, A. Gray-Weale, S. Perrier, "RAFT Polymerization Kinetics: Combination of Apparently Conflicting Models", Macromolecules, vol. 41, pp. 6400-6412, 2008.
[64] C. Barner-Kowollik, G. T. Russell, "Chain-length-dependent termination in radical polymerization: Subtle revolution in tackling a long-standing challenge", Progress in Polymer Science, vol. 34, pp. 1211-1259, 2008.
[65] J. Brandrup, E. Immergut, E. Grulke, Polymer Handbook, 4th ed., New York: Wiley, 1999.
[66] H. Fischer, L. Radom, "Factors Controlling the Addition of Carbon- Centered Radicals to Alkenes-An Experimental and Theoretical Perspective", Angew. Chem., Int. Ed., vol. 40, pp. 1340-1371, 2001.
[67] A. Feldermann, A. Ah Toy, H. Phan, M. H. Stenzel, T. P. Davis, C. Barner-Kowollik, "Reversible addition fragmentation chain transfer copolymerization: influence of the RAFT process on the copolymer composition", Polymer, vol. 45, pp. 3997-4007, 2004.