Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Journal of Chemical Physics

Volumn 117, Issue 14, 2002, Pages 6841-6851

  Ballone, P ^a,b   Jones, R O ^a  

^a FORSCHUNGSZENTRUM JÜLICH   (Germany)

^b UNIVERSITY OF MESSINA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONATE MINERALS; COMPUTER SIMULATION; GELS; MATHEMATICAL MODELS; MOLECULAR WEIGHT DISTRIBUTION; MONTE CARLO METHODS; ORGANIC POLYMERS; PHASE EQUILIBRIA; THERMAL EFFECTS; THREE DIMENSIONAL; TWO DIMENSIONAL;

CHAIN BRANCHING; CYCLIC CARBONATE OLIGOMERS; EQUILIBRIUM POLYMERIZATION; GEL TRANSITION; LENNARD-JONES PARTICLES; TRIFUNCTIONAL MONOMERS;

RING OPENING POLYMERIZATION;

EID: 0037044519     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1505023     Document Type: Article

References (45)

1. G. R. Strobl, The Physics of Polymers: Concepts for Understanding Their Structures and Behavior (Springer, Berlin, 1996).
2. L. Stryer, Biochemistry, 4th ed. (Freeman, New York, 1995). A discussion of glycogen is given on p. 587. Branching is an essential feature of this polymer, as it increases its solubility as well as its rate of degradation to glucose l-phosphate.
3. Low-density polyethylene produced by free-radical polymerization acquires branching points via a parasitic chain transfer reaction. P. Ehrlich, Adv. Polym. Sci. 7, 386 (1970)
4. R. C. M. Zabisky, W.-M. Chan, P. E. Glor, and A. E. Hamielec, Polymer 33, 2243 (1992)
5. P. Lorenzini, M. Pons, and J. Villermaux, Chem. Eng. Sci. 47, 3969 (1992).
6. S. M. Clarke, A. Hotta, A. R. Tajbakhsh, and E. M. Terentjev, Phys. Rev. E 64, 061702 (2001). The anisotropic mechanical behavior of liquid crystal elastomers depends on the way the networks are cross-linked.
7. H. O. Krabbenhoft and E. P. Boden, Makromol. Chem., Macromol. Symp. 42/43, 167 (1991). Branching in BPA-PC leads to high heat resistance and high shear sensitivity.
8. P. G. de Gennes, Scaling Concepts in Polymer Physics (Cornell University Press, Ithaca, 1979).
9. For discussions of these and related topics, see Kinetics of Aggregation and Gelation, edited by F. Family and D. P. Landau (North-Holland, Amsterdam, 1984).
10. For reviews of equilibrium polymerization and related topics, see M. E. Cates and S. J. Candau, J. Phys.: Condens. Matter 2, 6869 (1990)
11. S. C. Greer, J. Phys. Chem. B 102, 5413 (1998).
12. S. C. Greer, Adv. Chem. Phys. 94, 261 (1996).
13. Computer simulations studies of equilibrium polymers are reviewed in (a) J. P. Wittmer, P. van der Schoot, A. Milchev, and J. L. Barrat, J. Chem. Phys. 113, 6992 (2000)
14. (b) A. Milchev, J. P. Wittmer, and D. Landau, Phys. Rev. E 61, 2959 (2000)
15. (c) J. P. Wittmer, A. Milchev, and M. E. Cates, J. Chem. Phys. 109, 834 (1998).
16. M. Nosaka, M. Takasu, and K. Katoh, J. Chem. Phys. 115, 11333 (2001).
17. P. Ballone and R. O. Jones, J. Chem. Phys. 115, 3895 (2001).
18. P. Ballone and R. O. Jones, J. Chem. Phys. 116, 7724 (2002).
19. D. J. Brunelle, in Ring-Opening Polymerization: Mechanisms, Catalysis, Structure, Utility, edited by D. J. Brunelle (Hanser, München, Germany, 1993), p. 309.
20. P. J. Flory, J. Am. Chem. Soc. 63, 3083 (1941)
21. P. J. Flory, J. Am. Chem. Soc. 63, 3091 (1941)
22. P. J. Flory, J. Am. Chem. Soc. 63, 3096 (1941).
23. W. H. Stockmayer, J. Chem. Phys. 11, 45 (1943).
24. Most simulation studies of kinetic gelation use the bond fluctuation model of I. Carmesin and K. Kremer, Macromolecules 21, 2819 (1988)
25. E. Del Gado, L. de Arcangelis, and A. Coniglio, Phys. Rev. E 65, 041803 (2002) for a recent example.
26. A. Coniglio, H. E. Stanley, and W. Klein, Phys. Rev. Lett. 42, 518 (1979).
27. H. J. Herrmann, D. P. Landau, and D. Stauffer, Phys. Rev. Lett. 49, 412 (1982).
28. Y. Liu and R. B. Pandey, Phys. Rev. B 55, 8257 (1997).
29. M. Vogt and R. Hernandez, J. Chem. Phys. 115, 1575 (2001).
30. H. Tobita, J. Polym. Sci., Part B: Polym. Phys. 39, 2960 (2001)
31. H. Tobita, J. Polym. Sci., Part B: Polym. Phys. 39, 391 (2001)
32. R. A. Hutchinson, Macromol. Theory Simul. 10, 144 (2001).
33. J. B. Hutchinson and K. S. Anseth, Macromol. Theory Simul. 10, 600 (2001)
34. H. Tobita, N. Aoyagi, and S. Takamura, Polymer 42, 7583 (2001).
35. P. Ballone, B. Montanari, and R. O. Jones, J. Phys. Chem. A 104, 2793 (2000)
36. P. Ballone and R. O. Jones, ibid. 105, 3008 (2001).
37. The restriction to fixed bonding configurations avoids the discontinuous energy changes that occur on bond interchange. It could be removed by using more sophisticated rules or a different MD algorithm.
38. D. Stauffer, J. Chem. Soc., Faraday Trans. 2 72, 1354 (1976).
39. O. G. Mouritsen, Computer Studies of Phase Transitions and Critical Phenomena (Springer, Berlin, 1994).
40. L. Schäfer, Phys. Rev. B 46, 6061 (1992)
41. P. D. Gujrati, ibid. 40, 5140 (1989). In these models the number of chain terminations is not constant, but is determined by thermal equilibrium.
42. 1 is very low and is neglected.
43. Y. U. Lee, S. S. Jang, and W. H. Jo, Macromol. Theory Simul. 9, 188 (2000). Another type of inhomogeneous gel phase (micro-gels) results from the formation of distinct, large molecular aggregates with a high degree of cross-linking.
44. l(L)> shows, however, that our gel phase contains only one large crosslinked molecule.
45. Reference 20 discusses the characteristic differences between reversible and irreversible gelation.