Journal of Inorganic and Organometallic Polymers

, Volume 6, Issue 3, pp 237–253 | Cite as

Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2] n

  • Maria E. Amato
  • Antonio Grassi
  • Kenny B. Lipkowitz
  • Giuseppe M. Lombardo
  • Giuseppe C. Pappalardo
  • Claudia Sadun
Article
Received:
Revised:

Abstract

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP2NCl5 and OP3N2Cl5) were compared with those derived fromab initio quantum mechanics using the 6–31G* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; β=111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.

Key Words

Polyphosphazenes molecular dynamics poly[bis(chloro)phosphazene] force field parameters (CHARMM) 
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References

  1. 1.
    G. S. Kyker and T. A. Antkowiak,Rubber Chem. Technol. 47, 32 (1974).Google Scholar
  2. 2.
    D. P. Tate,J. Polym. Sci. Polym. Symp. 48, 33 (1974).Google Scholar
  3. 3.
    H. R. Allcock,Phosphorus-Nitrogen Compounds (Academic Press, New York, 1972).Google Scholar
  4. 4.
    J. F. Thompson and K. A. Reynard,J. Appl. Polym. Sci. 21, 2575 (1977).Google Scholar
  5. 5.
    A. H. Dikdwardo, I. Zitomer, D. Stuetz, R. F. Singler, and D. Macaione,Org. Coat. Prep. 36, 737 (1976).Google Scholar
  6. 6.
    H. R. Allcock, J. A. Dodge, L. S. Van Dyke, and C. R. Martin,Chem. Mater. 4, 780 (1992).Google Scholar
  7. 7.
    T. Kimura and M. Kajiwara,J. Inorg. Organomet. Polym. 2, 431 (1992).Google Scholar
  8. 8.
    K. Inoue, Y. Nishikawa, and T. Tanigaki,Macromolecules 24, 3464 (1991).Google Scholar
  9. 9.
    K. Inoue, Y. Nishikawa, and T. Tanigaki,J. Am. Chem. Soc. 113, 7609 (1991).Google Scholar
  10. 10.
    S. Ganapathiappan, K. Chen, and D. F. Shriver,J. Am. Chem. Soc. 111, 4091 (1989).Google Scholar
  11. 11.
    R. A. Saraceno, G. H. Riding, H. R. Allcock, and E. G. Ewing,J. Am. Chem. Soc. 110, 980 (1988).Google Scholar
  12. 12.
    R. A. Saraceno, G. H. Riding, H. R. Allcock, and E. G. Ewing,J. Am. Chem. Soc. 110, 7254 (1988).Google Scholar
  13. 13.
    K. Moriya, S. Miyata, S. Yano, and M. Kajiwara,J. Inorg. Organomet. Polym. 2, 443 (1992).Google Scholar
  14. 14.
    R. Singler, R. A. Willingham, C. Noel, C. Friedrich, L. Bosio, and E. D. T. Atkins,Macromolecules 24, 510 (1991).Google Scholar
  15. 15.
    H. R. Allcock and C. Kim,Macromolecules 23, 3881 (1990).Google Scholar
  16. 16.
    C. Kim and H. R. Allcock,Macromolecules 20, 1726 (1987).Google Scholar
  17. 17.
    H. R. Allcock, A. A. Dembek, C. Kim, R. L. S. Devine, Y. Shi, W. H. Steier, and C. W. Spangler,Macromolecules 24, 1000 (1991).Google Scholar
  18. 18.
    A. A. Dembek, C. Kim, H. R. Allcock, R. L. S. Devine, W. H. Steier, and C. W. Spangler,Chem. Mater. 2, 97 (1990).Google Scholar
  19. 19.
    E. J. Quinn, B. M. Althouse, and P. Potin, inProc. Symp. Chem. Comb. Toxic MARM, Millerville, PA, May (1988).Google Scholar
  20. 20.
    H. R. Allcock, inBiodegradable Polymers as Drug Delivery Systems, M. Chasin and R. Langer, eds. (Marcel Dekker, New York, 1990), p. 163.Google Scholar
  21. 21.
    H. R. Allcock, C. J. Nelson, W. D. Coggio, I. Manners, W. J. Koros, D. R. B. Walker, and L. A. Pessan,Macromolecules 26, 1493 (1993).Google Scholar
  22. 22.
    S. N. Gacta, H. C. Zhang, E. Drioli, and A. Basile,Desalination 80, 181 (1991).Google Scholar
  23. 23.
    E. Drioli, S. M. Zhang, A. Basile, G. Golemme, S. N. Gaeta, and H. C. Zhang,Gas Separat. Purit. 5, 252 (1991).Google Scholar
  24. 24.
    C. W. R. Wade, S. Gourlay, R. Rice, A. Hegyeli, R. E. Singler, and J. White, inOrganometallic Polymers, C. E. Carraher, J. E. Sheats, and C. U. Pittman, eds. (Academic Press, New York, 1978), p. 289.Google Scholar
  25. 25.
    J. H. Goedemoed and K. DeGroot,Makromol. Chem. Macromol. Symp. 19, 341 (1988).Google Scholar
  26. 26.
    C. W. J. Grolleman, A. C. DeVisser, J. G. C. Wolke, H. Van der Goot, and H. Timmerman,J. Control. Release 3, 143 (1986).Google Scholar
  27. 27.
    C. W. J. Grolleman, A. C. DeVisser, J. G. C. Wolke, H. Van der Goot, and H. Timmerman.J. Control. Releasc 4, 133 (1986).Google Scholar
  28. 28.
    C. W. J. Grolleman, A. C. DeVisser, J. G. C. Wolke, H. Van der Goot, and H. Timmerman.J. Control. Releasc 4, 119 (1986).Google Scholar
  29. 29.
    T. X. Neenan and H. R. Allcock,Biomaterials 3, 78 (1982).PubMedGoogle Scholar
  30. 30.
    S. Lora, M. Carenza, G. Palma, G. Pezzin, P. Caliceti, P. Battaglia, and A. Lora.Biomaterials 12, 275 (1991).PubMedGoogle Scholar
  31. 31.
    H. R. Allcock, S. Kwon, G. H. Riding, R. J. Fitzpatrick, and J. L. Bennett.Biomaterials 9, 509 (1988).PubMedGoogle Scholar
  32. 32.
    M. P. Allen and D. J. Tildesley.Computer Simulations of Liquids (Clarendon Press, Oxford. 1987).Google Scholar
  33. 33.
    W. E. Van Gunsteren, P. K. Weiner, and A. J. Wilkinson (eds.).Computer Sunulation of Biomolecular Systems: Theorencal and Experimental Applications, Vol. 2 (ESCOM Science, Leiden, 1993).Google Scholar
  34. 34.
    B. R. Brooks, R. E. Bruccoleri, B. D. Olafson, D. J. States, S. Swaminathan, and M. Karplus.J Comput. Chem. 4, 187 (1983).Google Scholar
  35. 35.
    U. Burkert and N. L. Allinger.Molecular Mechanics. ACS Monograph 177 (American Chemical Society. Washington, DC, 1982).Google Scholar
  36. 36.
    R. Caminiti, M. Gleria, K. B. Lipkowitz, G. M. Lombardo, and G. C. Pappalardo.J. Am. Chem. Soc. (in press, 1997).Google Scholar
  37. 37.
    U. Dinur and A. T. Hagler, inReriews in Computational Chemistry, Vol. 2. K. B. Lipkowitz and D. B. Boyd, eds. VCH Publishers. New York, 1991). pp. 99–164.Google Scholar
  38. 38.
    M. E. Amato, K. B. Lipkowitz, G. M. Lombardo, and G. C. Pappalardo.J. Mol. Struct. 372, 69 (1995).Google Scholar
  39. 39.
    Y. Chatani and K. Yatsuyanagi.Macromolecules 20, 1042 (1987).Google Scholar
  40. 40.
    H. R. Allcock, R. W. Allen, and J. J. Meister.Macromolecules 9, 950 (1976).Google Scholar
  41. 41.
    M. J. Frish, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, N. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzales, R. L. Martin, D. J. Fox, D. J. DeFrees, J. Baker, J. J. P. Stewart, and J. A. Pople.GAUSSLAN 92, Revision D.2 (Gaussian Inc., Pittsburg, PA. 1993).Google Scholar
  42. 42.
    H. R. Allcock, N. M. Tollefson, R. A. Areus, and R. R. Whittle,J. Am. Chem. Soc. 107, 5166 (1985).Google Scholar
  43. 43.
    H. R. Allcock, R. A. Arcus, and E. D. Stroh.Macromolecules 13, 919 (1980).Google Scholar
  44. 44.
    E. Giglio, F. Pompa, and A. Ripamonti,J. Polym. Sci. 59, 293 (1962).Google Scholar
  45. 45.
    A. Grassi, G. M. Lombardo, and G. C. Pappalardo.J. Mol. Struct. THEOCHEM 311, 101 (1994).Google Scholar
  46. 46.
    S. V. Meille, A. R. Poletti, M. C. Gallazzi, M. Gleria, and S. Bruckner.Polymer 33, 2364 (1992).Google Scholar

Copyright information

© Plenum Publishing Corporation 1996

Authors and Affiliations

  • Maria E. Amato
    • 1
  • Antonio Grassi
    • 2
  • Kenny B. Lipkowitz
    • 3
  • Giuseppe M. Lombardo
    • 2
  • Giuseppe C. Pappalardo
    • 2
  • Claudia Sadun
    • 4
  1. 1.Dipartimento di Scienze ChimicheUniversitá di CataniaCataniaItaly
  2. 2.Dipartimento di Scienze Chimiche, Cattedra di Chimica Generale, Facoltá di FarmaciaUniversitá di CataniaCataniaItaly
  3. 3.Department of ChemistryIndiana University Purdue University at IndianapolisIndianapolis
  4. 4.Istituto Nazionale per la Fisica della Materia, Dipartimento di ChimicaUniversita La SapienzaRomaItaly

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