Abstract
In this paper we report first principles calculations using the Car-Parrinello molecular dynamics approach in order to clarify the mechanism of the ring-opening polymerization of hexachlorocyclotriphosphazene, N3P3Cl6 to polydichlorophosphazene (NPCl2) n . In particular, we highlight the key role played by the cyclophosphazene phosphorus cation N3P3Cl5 + generated from the heterolytic cleavage of the P–Cl bond as the main component in the polymerization process. Moreover, the generation of the maximally localized Wannier functions, together with the Mulliken population analysis, allows us to clarify some basic issues of the investigated reaction. The activation energy, mainly due to the formation of phosphazenium cation, is found to be in good agreement with experiments. Structural and electronic analysis of the molecules involved is also reported.
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H.R. Allcock, R.L. Kugel, K.J. Valan, Inorg. Chem. 5, 1709 (1966)
H. R. Allcock and R. L. Kugel, US, Ed., 1968
H.R. Allcock, R.L. Kugel, Inorg. Chem. 5, 1716 (1966)
H.R. Allcock, R.L. Kugel, J. Am. Chem. Soc. 87, 4216 (1965)
H.R. Allcock, Phosphorus–Nitrogen Compounds. Cyclic, Linear, and High Polymeric Systems (Academic Press, New York, 1972)
M. Gleria, R. De Jaeger, NOVA Science Publishers (Hauppauge, N.Y., 2004)
H.R. Allcock, Chemistry and Applications of Polyphosphazenes (John Wiley & Sons Inc., Hoboken, 2003)
A.K. Andrianov, J. Chen, M.P. LeGolvan, Macromolecules 37, 414 (2004)
P. Potin, R. Dejaeger, Eur. Polym. J. 27, 341 (1991)
G. Dhalluin, R. Dejaeger, J.P. Chambrette, P. Potin, Macromolecules 25, 1254 (1992)
R. De Jaeger, P. Potin, Phosphorus Sulfur and Silicon and the Related Elements 76, 483 (1993)
H.R. Allcock, C.A. Crane, C.T. Morrissey, J.M. Nelson, S.D. Reeves, C.H. Honeyman, I. Manners, Macromolecules 29, 7740 (1996)
H.R. Allcock, C.T. Morrissey, I. Manners, C.H. Honeyman, US 5,698,664 (1997), CAN 128, 75825t (1998), assigned to The Penn State Research Foundation
H.R. Allcock, J.M. Nelson, S.D. Reeves, C.H. Honeyman, I. Manners, Macromolecules 30, 50 (1997)
H.R. Allcock, S.D. Reeves, J.M. Nelson, C.A. Crane, I. Manners, Macromolecules 30, 2213 (1997)
J.M. Nelson, H.R. Allcock, I. Manners, Abstracts of Papers of the American Chemical Society 216, 259 (1998)
J.M. Nelson, A.P. Primrose, T.J. Hartle, H.R. Allcock, I. Manners, Macromolecules 31, 947 (1998)
H.R. Allcock, C.T. Morrissey, I. Manners, C.H. Honeyman, J.M. Nelson, C. Crane, S.D. Reeves, A.P. Primrose, T.J. Hartle, R. Prange, US 5,914,388 (1999), CAN 131, 32301 (1999), assigned to The Penn State Research Foundation, USA
H.R. Allcock, S.D. Reeves, J.M. Nelson, I. Manners, Macromolecules 33, 3999 (2000)
R. De Jaeger, M. Gleria, Prog. Polym. Sci. 23, 179 (1998)
M. Gleria, R. De Jaeger, Top. Curr. Chem. 250, 165 (2005)
V. Luaña, A.M. Pendas, A. Costales, G.A. Carriedo, F.J. Garcia Alonso, J. Phys. Chem. A 105, 5280 (2001)
H. Sabzyana, Z. Kalantar, J. Mol. Struct. 663, 149 (2003)
R. Jaeger, M. Debowski, I. Manners, G.J. Vancso, Inorg. Chem. 38, 1153 (1999)
M. Breza, Polyhedron 19, 389 (2000)
H. Sun, P. Ren, J.R. Fried, Comput. Theor. Polym. Sci. 8, 229 (1998)
L. Kapika, P. Kubácek, P. Holub, J. Mol. Struct. 820, 148 (2007)
M. Calichman, A. Derecskei-Kovacs, C.W. Allen, Inorg. Chem. 46, 2011 (2007)
P.L. Silvestrelli, M. Gleria, R. Milani, A. Boscolo-Boscoletto, J. Inorg. Organomet. Polym. 16, 327 (2006)
J.L. Kroger, J.R. Fried, J. Inorg. Organomet. Polym. 22, 973 (2012)
H.R. Allcock, Polymer 21, 673 (1980)
G.L. Hagnauer, J. Macromol. Sci. Chem. A16, 385 (1981)
Y. Zhang, K. Huynh, I. Manners, C.A. Reed, Chem. Commun., 494 (2008)
A.J. Heston, M.J. Panzner, W.J. Youngs, C.A. Tessier, Inorg. Chem. 44, 6518 (2005)
Z.M. Tun, A.J. Heston, M.J. Panzner, D.A. Medvetz, B.D. Wright, D. Savant, V.R. Dudipala, D. Banerjee, P.L. Rinaldi, W.J. Youngs, C.A. Tessier, Inorg. Chem. 50, 8937 (2011)
E. Lork, P.G. Watson, R. Mews, J. Chem. Soc. Chem Commun., 1717 (1995)
R. Car, M. Parrinello, Phys. Rev. Lett. 55, 2471 (1985)
J. Hutter, A. Alavi, T. Deutch, M. Bernasconi, S. Goedecker, D. Marx, M. Tuckerman, M. Parrinello, CPMD MPI für Festköperforschung and IBM Zurich Research Laboratory, Stuttgart (1995–1999)
F. Patat, K. Frömbling, Monatsh 86, 718 (1955)
F. Patat, P. Derst, Angew. Chem. 71, 105 (1959)
F.G.R. Gimblett, Plast. Inst. (London) Trans. J. 28, 65 (1960)
D. Chakrabartty, B.N. Ghosh, J. Polym. Sci. 62, S130 (1962)
J.R. Soulen, M.S. Silverman, J. Polym. Sci. 1, 823 (1963)
J.R. MacCallum, A. Werninck, J. Polym. Sci. 5, 3061 (1967)
J.E.A. Hutter, Computer code CPMD, version 3.12.0; Copyright IBM Corp. and MPI-FKF Stuttgart; http://www.cpmd.org (1990–2007)
A.D. Becke, J. Chem. Phys. 98, 5648 (1993)
C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785 (1988)
N. Troullier, J.L. Martins, Phys. Rev. B 43, 1993 (1991)
A. Wilson, D.F. Carrol, J. Chem. Soc., 2548 (1960)
G.J. Bullen, J. Chem. Soc., 1450 (1971)
A. Schulz, M. Thormählen, H.C. Müller, Internet Electron J. Mol. Des. 2, 653 (2003)
A.B. Chaplin, J.A. Harrison, P.J. Dyson, Inorg. Chem. 44, 8407 (2005)
C. Moller, M.S. Plesset, Phys. Rev. 46, 618 (1934)
R.J. Bartlett, Ann. Rev. Phys. Chem. 32, 359 (1981)
J. Hutter, H.P. Luthi, M. Parrinello, Comput. Mater. Sci. 2, 244 (1994)
M.C. Payne, M.P. Teter, D.C. Allan, T.A. Arias, J.D. Joannopoulos, Rev. Mod. Phys. 64, 1045 (1992)
P.L. Silvestrelli, M. Parrinello, Phys. Rev. Lett. 82, 3308 (1999)
P.L. Silvestrelli, Phys. Rev. B 59, 9703 (1999)
M. Mugnai, G. Cardini, V. Schettino, J. Chem. Phys. 120, 5327 (2004)
N. Marzari, D. Vanderbilt, Phys. Rev. B 56, 12487 (1997)
P.L. Silvestrelli, N. Marzari, D. Vanderbilt, M. Parrinello, Solid State Commun. 107, 7 (1998)
G.H. Wannier, Phys. Rev. 52, 191 (1937)
M. Boero, M. Parrinello, S. Hüffer, H. Weiss, J. Am. Chem. Soc. 122, 501 (2000)
D. Aktah, D. Passerone, M. Parrinello, J. Phys. Chem. A 108, 848 (2004)
T. Kupka, K. Pasterny, G. Pasterna, K. Brandt, J. Mol. Struct. 866, 21 (2008)
Y. Zhang, F.S. Tham, C.A. Reed, Inorg. Chem. 45, 10446 (2006)
C.A. Reed, K.C. Kim, E.S. Stoyanov, D. Stasko, F.S. Tham, L.J. Mueller, P.D.W. Boyd, J. Am. Chem. Soc. 125, 1796 (2003)
S. Bilge, Turkish J. Chem. 35, 745 (2011)
H.R. Allcock, J.E. Gardner, K.M. Smeltz, Macromolecules 8, 36 (1975)
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Costanzo, F., Silvestrelli, P.L., Gleria, M. et al. The Thermally-Induced Bulk Polymerization of Hexachlorocyclotriphosphazene to Polydichlorophosphazene by First-Principles Simulations. J Inorg Organomet Polym 23, 1397–1408 (2013). https://doi.org/10.1007/s10904-013-9942-6
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DOI: https://doi.org/10.1007/s10904-013-9942-6