Multiscale Modeling of Branch Length in Butyl Acrylate Solution Polymerization
Jonathan A. Rawlston
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA
Search for more papers by this authorFrancis Joseph Schork
University of Maryland, Department of Chemical and Biomolecular Engineering, 2113 Chemical and Nuclear Engineering, College Park, Maryland 20742, USA
Search for more papers by this authorCorresponding Author
Martha A. Grover
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA. Fax: (+404) 894 2866Search for more papers by this authorJonathan A. Rawlston
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA
Search for more papers by this authorFrancis Joseph Schork
University of Maryland, Department of Chemical and Biomolecular Engineering, 2113 Chemical and Nuclear Engineering, College Park, Maryland 20742, USA
Search for more papers by this authorCorresponding Author
Martha A. Grover
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332, USA. Fax: (+404) 894 2866Search for more papers by this authorAbstract
Branch lengths resulting from both backbiting and intermolecular chain transfer to polymer are examined for the solution polymerization of butyl acrylate, using a rate-equation model and ordinary differential equations. Backbiting is allowed to generate branches of varying length, according to a cumulative distribution function obtained from a lattice kinetic Monte Carlo simulation. About 8% of the branches produced by backbiting are 10 mers or longer. In contrast to common assumptions about the origins of short-chain and long-chain branches, the model indicates that nearly all of the long-chain branches may be produced by backbiting, rather than intermolecular chain transfer to polymer.
References
- 1 C. Plessis, G. Arzamendi, J. R. Leiza, H. A. S. Schoonbrood, D. Charmot, J. M. Asua, Macromolecules 2001, 34, 5147.
- 2 N. M. Ahmad, P. A. Lovell, S. M. Underwood, Polym. Int. 2001, 50, 625.
- 3 C. Former, J. Castro, C. M. Fellows, R. I. Tanner, R. G. Gilbert, J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 3335.
- 4 N. M. Ahmad, F. Heatley, P. A. Lovell, Macromolecules 1998, 31, 2822.
- 5 O. J. Karlsson, J. M. Stubbs, R. H. Carrier, D. C. Sundberg, Polym. React Eng. 2003, 11, 589.
- 6 F. Teymour, J. D. Campbell, Macromolecules 1994, 27, 2460.
- 7 P. Pladis, C. Kiparissides, Chem. Eng. Sci. 1998, 53, 3315.
- 8 A. Krallis, C. Kiparissides, Chem. Eng. Sci. 2007, 62, 5304.
- 9 P. D. Iedema, S. Grcev, H. C. J. Hoefsloot, Macromolecules 2003, 36, 458.
- 10 D. M. Kim, P. D. Iedema, Chem. Eng. Sci. 2008, 63, 2035.
- 11 C. Plessis, G. Arzamendi, J. R. Leiza, H. A. S. Schoonbrood, D. Charmot, J. M. Asua, Macromolecules 2000, 33, 5041.
- 12 Y. Liu, W. F. Schroeder, J. C. Haley, W. Lau, M. A. Winnik, Macromolecules 2008, 41, 9104.
- 13 F. S. Rantow, M. Soroush, M. C. Grady, G. A. Kalfas, Polymer 2006, 47, 1423.
- 14 P. Castignolles, R. Graf, M. Parkinson, M. Wilhelm, M. Gaborieau, Polymer 2009, 50, 2373.
- 15 C. Plessis, G. Arzamendi, J. R. Leiza, J. M. Alberdi, H. A. S. Schoonbrood, D. Charmot, J. M. Asua, J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 1106.
- 16 A. N. Nikitin, R. A. Hutchinson, G. A. Kalfas, J. R. Richards, C. Bruni, Macromol. Theory Simul. 2009, 18, 247.
- 17 C. Plessis, G. Arzamendi, J. R. Leiza, H. A. S. Schoonbrood, D. Charmot, J. M. Asua, Ind. Eng. Chem. Res. 2001, 40, 3883.
- 18 G. Arzamendi, J. R. Leiza, Ind. Eng. Chem. Res. 2008, 47, 5934.
- 19 G. Arzamendi, C. Plessis, J. R. Leiza, J. M. Asua, Macromol. Theory Simul. 2003, 12, 315.
- 20 G. Moad, D. H. Solomon, The Chemistry of Radical Polymerization, 2nd edition, Elsevier, Oxford 2006.
- 21 C. H. Bamford, R. W. Dyson, G. C. Eastmond, Polymer 1969, 10, 885.
- 22 J. M. Asua, S. Beuermann, M. Buback, P. Castignolles, B. Charleux, R. G. Gilbert, R. A. Hutchinson, J. R. Leiza, A. N. Nikitin, J. P. Vairon, A. M. van Herk, Macromol. Chem. Phys. 2004, 205, 2151.
- 23 C. Barner-Kowollik, F. Guenzler, T. Junkers, Macromolecules 2008, 41, 8971.
- 24 S. Maeder, R. G. Gilbert, Macromolecules 1998, 31, 4410.
- 25 A. N. Nikitin, R. A. Hutchinson, M. Buback, P. Hesse, Macromolecules 2007, 40, 8631.
- 26 M. Stickler, G. Meyerhoff, Makromol. Chem. 1978, 179, 2729.
- 27 S. Beuermann, M. Buback, T. P. Davis, R. G. Gilbert, R. A. Hutchinson, O. F. Olaj, G. T. Russell, J. Schweer, A. M. vanHerk, Macromol. Chem. Phys. 1997, 198. 1545.
- 28 S. Beuermann, M. Buback, Prog. Polym. Sci. 2002, 27, 191.
- 29 A. N. Nikitin, R. A. Hutchinson, Macromol. Theory Simul. 2006, 15, 128.
- 30 J. Blomqvist, L. O. Pietila, B. Mannfors, Polymer 2001, 42, 109.
- 31 R. B. Karyappa, U. Natarajan, J. Macromol. Sci., Part B: Phys. 2008, 47, 1075.
- 32 R. D. Peralta, R. Infante, G. Cortez, L. E. Elizalde, J. Wisniak, Thermochim. Acta 2004, 421, 59.
- 33 P. J. Flory, J. Chem. Phys. 1949, 17, 303.
- 34 K. Binder, J. Baschnagel, W. Paul, Prog. Polym. Sci. 2003, 28, 115.
- 35 J. Molina-Mateo, J. M. Meseguer Duenas, J. L. Gomez Ribelles, C. Torregrosa Cabanilles, Polymer 2009, 50, 5618.
- 36 F. T. Wall, L. A. Hiller, D. J. Wheeler, J. Chem. Phys. 1954, 22, 1036.
- 37 F. A. Bovey, F. C. Schilling, F. L. McCrackin, H. L. Wagner, Macromolecules 1976, 9, 76.
- 38 B. H. Zimm, W. H. Stockmayer, J. Chem. Phys. 1949, 17, 1301.
- 39 F. W. Billmeyer, Jr., Textbook of Polymer Science, 3rd edition, Wiley, New York 1984, p. 211.
- 40 M. Kurata, Y. Tsunashima, Viscosity-Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules, in: Polymer Handbook, J. Brandrup, E. H. Immergut, E. A. Grulke, Eds., 4th edition, Wiley & Sons, New York 1999, p. VII/12.
- 41 G. Kraus, C. J. Stacy, J. Polym. Sci., Polym. Symp. 1973, 329.
- 42 D. S. Achilias, C. Kiparissides, Macromolecules 1992, 25, 3739.
- 43 P. Hesse, PhD thesis 2008, University of Gottingen.
