A New Approach for Monte Carlo Simulation of RAFT Polymerization

Document Type : Research Article

Authors

1 Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, I.R. IRAN

2 Department of Polymer Engineering, Sahand University of Technology, P.O. Box 51335-1996, Tabriz, I.R. IRAN

Abstract

In this work, based on experimental observations and exact theoretical predictions, the kinetic scheme of RAFT polymerization is extended to a wider range of reactions such as irreversible intermediate radical terminations and reversible transfer reactions. The reactions which have been labeled as kinetic scheme are the more probable existing reactions as the theoretical point of view. The detailed kinetic scheme is applied to three kinds of RAFT polymerization system by utilizing the Monte Carlo simulation Method. To do this, a new approach of simulation method was used. In this approach, a multi-reaction step was used in each time step. Unknown kinetic rate constants have obtained by curve fitting of the simulation results and theoretical data, applying the least square method; or estimated by considering theoretical facts and experimental findings. The origin of the rate retardation and induction period has been understood by studying the main and pre-equilibrium stages of dithiobenzoate-mediated RAFT homo polymerization. A copolymerization system in the presence of RAFT agent has also been examined to confirm the capability of introduced simulation method in different monomer/RAFT agent systems. The simulation results were in excellent agreement with experimental data, which proves the validity and applicability of the Monte Carlo algorithm.  

Keywords

Main Subjects

References

[1] Chiefari J., Chong Y.K., Ercole F., Krstina J., Jeffery J., Le T.P.T., Mayadunne R.T.A., Meijs G.F., Moad C.L., Moad G., Rizzardo E., Thang S.H., Living Free-Radical Polymerization by Reversible Addition Fragmentation Chain Transfer: The RAFT Process, Macromolecules, 31, p. 5559 (1998).
[2] Salami-Kalajahi M., Haddadi-Asl V., Ganjeh-Anzabi P., Najafi M., Dithioester-mediated RAFT Polymerization: A Kinetic Study by Mathematical Modelling, Iran Polym. J., 20, p. 459 (2011).
[3] Schilli C.M., Zhang M., Rizzardo E., Thang S.H., Chong Y.K., Edwards K., Karlsson G., Mueller A.H.E., A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid), Macromolecules, 37, p. 7861 (2004).
[4] Sun X., Luo Y., Wang R., Li B., Liu B., Zhu S., Programmed Synthesis of Copolymer with Controlled Chain Composition Distribution via Semibatch RAFT Copolymerization, Macromolecules, 40, p. 849 (2007).
[5] Mayadunne R.T.A., Jeffery J., Moad G., Rizzardo E., Living Free Radical Polymerization with Reversible Addition Fragmentation Chain Transfer (RAFT Polymerization): Approaches to Star Polymers, Macromolecules, 36, p. 1505 (2003).
[6] Perrier S., Takolpuckdee P., Macromolecular Design via Reversible Addition-Fragmentation Chain Transfer (RAFT)/Xanthates (MADIX) Polymerization, J. Polym. Sci., Part A: Polym. Chem., 43, p. 5347 (2005).
[7] Feldermann A., Coote M. L., Stenzel M.H., Davis T.P., Barner-Kowollik C., Consistent Experimental and Theoretical Evidence for Long-Lived Intermediate Radicals in Living Free Radical Polymerization, J. Am. Chem. Soc., 126, p. 15915 (2004).
[8] Buback M., Vana P., Mechanism of Dithiobenzoate-Mediated RAFT Polymerization: A Missing Reaction Step, Macromol. Rapid Commun., 27, p. 1299 (2006).
[9] McLeary J.B., Calitz F.M., McKenzie J.M., Tonge M.P., Sanderson R.D., Klumperman B., A 1H NMR Investigation of Reversible Addition Fragmentation Chain Transfer Polymerization Kinetics and Mechanisms. Initialization with Different Initiating and Leaving Groups, Macromolecules, 38, p. 3151 (2005).
[10] McLeary J.B., Calitz F.M., McKenzie J.M., Tonge M.P., Sanderson R.D., Klumperman B., Beyond Inhibition: A 1H NMR Investigation of the Early Kinetics of RAFT-Mediated Polymerization with the Same Initiating and Leaving Groups, Macromolecules, 37, p. 2383 (2004).
[11] Coote M.L., Izgorodina E.I., Krenske E.H., Busch M., Barner-Kowollik C., Quantum Chemical Mapping of Initialization Processes in RAFT Polymerization, Macromol. Rapid Commun., 27, p. 1015 (2006).
[12] Konkolewicz D., Hawkett B.S., Gray-Weale A., Perrier S., RAFT Polymerization Kinetics: Combination of Apparently Conflicting Models, Macromolecules, 41, p. 6400 (2008).
[13] Prescott S.W., Ballard M.J., Rizzardo E., Gilbert R.G., Rate Optimization in Controlled Radical Emulsion Polymerization Using RAFT, Macromol. Theory Simul., 15, p. 70 (2006).
[14] Wang A.R., Zhu S., Modeling the Reversible Addition–Fragmentation Transfer Polymerization Process, J. Polym. Sci., Part A: Polym. Chem., 41, p. 1553 (2003).
[15] Tobita H., Yanase F., Monte Carlo Simulation of Controlled/Living Radical Polymerization in Emulsified Systems, Macromol. Theory Simul., 16, p. 476 (2007).
[16] Salami-Kalajahi M., Haddadi-Asl V., Najafi M., Ghafelebashi-Zarand S.M., Investigation of Ethylene Polymerization Kinetics over Ziegler-Natta Catalysts: Employing Moment Equation Modeling to Study the Effect of Different Active Centers on Homopolymerization Kinetics, E-polymers., 004, (2008).
[17] Kwak Y., Goto A., Tsujii Y., Murata Y., Komatsu K., Fukuda T., A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition Fragmentation Chain Transfer, Macromolecules, 35, p. 3026 (2002).
[18] Salami-Kalajahi M., Najafi M., Haddadi-Asl V., Application of Monte Carlo Simulation Method to Polymerization Kinetics over Ziegler-Natta Catalysts, Int. J. Chem. Kinet., 41, p. 45 (2009).
[19] Najafi M., Haddadi-Asl V., Salami-Kalajahi M., Roghani-Mamaqani H., Application of the Monte Carlo Simulation Method to the Investigation of the Effect of Chain-Length-Dependent Bimolecular Termination on ATRP, E-polymers, 030 (2009).
[20] Mahjub A., Salami-Kalajahi M., Haddadi-Asl V., Roghani-Mamaqani H., Monte Carlo Simulation of Photo-Initiated Bulk Polymerization of Furfuryl Methacrylate, Iran Polym. J., 20, p. 205 (2011).
[21] Najafi M., Roghani-Mamaqani H., Salami-Kalajahi M., Haddadi-Asl V., A Simulation of Kinetics and Chain Length Distribution of Styrene FRP and ATRP: Chain-Length-Dependent Termination, Adv. Polym. Tech., 30, p.257 (2011).
[22] Najafi M., Salami-Kalajahi M., Haddadi-Asl V., Quantitative Evaluation of Arrangement of Monomers in Linear Binary Copolymers Using a Monte CarloSimulation Method, Chinese J. Polym. Sci., 27, p. 195 (2009).
[23] Khubi-Arani Z., Salami-Kalajahi M., Najafi M., Roghani-Mamaqani H., Haddadi-Asl V., Ghafelebashi-Zarand S.M., Simulation of Styrene Free Radical Polymerization over Bi-Functional Initiators Using Monte Carlo Simulation Method and Comparison with Mono-Functional Initiators, Polym. Sci. Ser. B, 52, p. 184 (2010).
[24] Najafi M., Roghani-Mamaqani H., Salami-Kalajahi M., Haddadi-Asl V., A Comprehensive Monte CarloSimulation of Styrene Atom Transfer Radical Polymerization, Chinese J. Polym. Sci., 28, p. 483 (2010).
[25] Najafi M., Roghani-Mamaqani H., Salami-Kalajahi M., Haddadi-Asl V., An Exhaustive Study of Chain-Length-Dependent and Diffusion-Controlled Free Radical and Atom-Transfer Radical Polymerization of Styrene, J. Polym. Res., 18, p. 1539 (2011).
[26] Barner-Kowollik C., Buback M., Charleux B., Coote M.L., Drache M., Fukuda T., Goto A., Klumperman B., Lowe A.B., McLeary J.B., Moad G., Monteiro M.J., Sanderson R.D., Tonge M.P., Vana P., Mechanism and Kinetics of Dithiobenzoate-Mediated RAFT Polymerization. I. The Current Situation, J. Polym. Sci., Part A: Polym. Chem., 44, p. 5809 (2006).
[27] Kwak Y., Goto A., Fukuda T., Rate Retardation in Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization: Further Evidence for Cross-Termination Producing 3-Arm Star Chain, Macromolecules, 37, p. 1219 (2004).
[28] Feldermann A., Ah Toy A., Phan H., Stenzel M.H., Davis T.P., Barner-Kowollik C., Reversible Addition Fragmentation Chain Transfer Copolymerization: Influence of the RAFT Process on the Copolymer Composition, Polymer, 45, p. 3997 (2004).
 
Iranian Journal of Chemistry and Chemical Engineering
Volume 31, Issue 3 - Serial Number 63
September 2012
Pages 75-84

Files

Share

How to cite

Statistics