Monte Carlo simulation on kinetics of batch and semi-batch free radical polymerization

Jing Shao; Wei Tang; Ru Xia; Xiaoshuang Feng; Peng Chen; Jiasheng Qian; Changjiang Song

Macromolecular Research, Vol.23, No.11, 1042-1050, November, 2015

DOI10.1007/s13233-015-3136-8 Export Citation

Monte Carlo simulation on kinetics of batch and semi-batch free radical polymerization

Jing Shao, Wei Tang, Ru Xia^†, Xiaoshuang Feng¹, Peng Chen^†, Jiasheng Qian, and Changjiang Song²

Anhui Province Key Laboratory of Environment-friendly Polymer Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei, 230601, P. R. China
¹Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia
²Anhui Zhongyi Rubber Belts Co, Ltd, Huaibei, 235000, P. R. China

E-mail:,

Based on Monte Carlo simulation technology, we proposed a hybrid routine which combines reaction mechanism together with coarse-grained molecular simulation to study the kinetics of free radical polymerization. By comparing with previous experimental and simulation studies, we showed the capability of our Monte Carlo scheme on representing polymerization kinetics in batch and semi-batch processes. Various kinetics information, such as instant monomer conversion, molecular weight, and polydispersity etc. are readily calculated from Monte Carlo simulation. The kinetic constants such as polymerization rate k p is determined in the simulation without of “steady-state” hypothesis. We explored the mechanism for the variation of polymerization kinetics those observed in previous studies, as well as polymerization-induced phase separation. Our Monte Carlo simulation scheme is versatile on studying polymerization kinetics in batch and semi-batch processes.

Keywords:Monte Carlo simulation;free radical polymerization;semi-batch;kinetics

[References]

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[2] Wang D, Li X, Wang WJ, Gong X, Li BG, Macromolecules, 45, 28 (2011)

[3] Boutevin B, J. Polym. Sci. A: Polym. Chem., 38(18), 3235 (2000)

[4] Nogueira AL, Lona LMF, Machado RAF, J. Appl. Polym. Sci., 91(2), 871 (2004)

[5] Clites JS, Colvin HA, Fiedler RD, Continuous Polymerization Process, EP Patent 0936232Al, 1999.

[6] Alb AM, Reed WF, Macromol. React. Eng., 4, 470 (2010)

[7] Beuermann S, Buback M, Prog. Polym. Sci, 27, 191 (2002)

[8] Alb AM, Reed WF, Macromolecules, 42(21), 8093 (2009)

[9] Dotson N, Galvan R, Laurence R, Tirrell M, Polymerization Process Modeling, 1st ed., Wiley-VCH, New York, 1995.

[10] Wulkow M, Macromol. React. Eng., 2, 461 (2008)

[11] Cuccato D, Mavroudakis E, Dossi M, Moscatelli D, Macromol. Theory Simul., 22, 127 (2013)

[12] Akkermans RLC, Toxvaerd S, Briels WJ, J. Chem. Phys., 109(7), 2929 (1998)

[13] Lu W, Ding J, Acta Chim. Sin., 63, 1231 (2005)

[14] Lu W, Ding J, Sci. China Ser. B, 35, 27 (2005)

[15] Lu WQ, Ding JD, Macromolecules, 39(21), 7433 (2006)

[16] Genzer J, Macromolecules, 39(20), 7157 (2006)

[17] Tomlinson MR, Efimenko K, Genzer J, Macromolecules, 39(26), 9049 (2006)

[18] Turgman-Cohen S, Genzer J, Macromolecules, 43(22), 9567 (2010)

[19] Turgman-Cohen S, Genzer J, J. Am. Chem. Soc., 133(44), 17567 (2011)

[20] Turgman-Cohen S, Genzer J, Macromolecules, 45(4), 2128 (2012)

[21] He XH, Tang J, J. Polym. Sci. A: Polym. Chem., 46(13), 4486 (2008)

[22] Wang L, He XH, J. Polym. Sci. A: Polym. Chem., 47(2), 523 (2009)

[23] Yang XM, Wang L, He XH, J. Polym. Sci. A: Polym. Chem., 48(22), 5072 (2010)

[24] Lattuada M, Del Gado E, Abete T, de Arcangelis L, Lazzari S, Diederich V, Storti G, Morbidelli M, Macromolecules, 46(15), 5831 (2013)

[25] Lisal M, Brennan JK, Smith WR, J. Chem. Phys., 125, 164905 (2006)

[26] Lisal M, Brennan JK, Smith WR, J. Chem. Phys., 130, 104902 (2009)

[27] Liu H, Lu Z, Front. Chem. China, 6, 300 (2011)

[28] Carmesin I, Kremer K, Macromolecules, 21, 2819 (1998)

[29] Deutsch HP, Dickman R, J. Chem. Phys., 93, 8983 (1990)

[30] Santanakrishnan S, Tang L, Hutchinson RA, Stach M, Lacik I, Schrooten J, Hesse P, Buback M, Macromol. React. Eng., 4, 499 (2010)

[31] Cutie SS, Smith PB, Henton DE, Staples TL, Powell C, J. Polym. Sci. B: Polym. Phys., 35(13), 2029 (1997)

[32] Stach M, Lacik I, Chorvat D, Buback M, Hesse P, Hutchinson RA, Tang L, Macromolecules, 41(14), 5174 (2008)