Abstract.
We model a melt of monodisperse side-chain liquid-crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded-volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free-energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases or phases with modulated wave vector but without nematic ordering. Such microphases are the result of the competition between the incompatibility among the blocks and the connectivity constraints imposed by the spacer and the backbone. Also the effects of the polymerization degree and structural conformation of the monomeric units on the phase behavior of the side-chain liquid-crystalline polymers are studied.
Similar content being viewed by others
References
V.P. Shibaev, N.A. Platé, Adv. Polym. Sci. 60, 173 (1984).
M. Lee, B. Cho, W. Zin, Chem. Rev. 101, 3869 (2001).
N. Yamazaki, M. Motoyama, M. Nonomura, T. Ohta, J. Chem. Phys. 120, 3949 (2004).
V. Pryamitsyn, V. Ganesan, J. Chem. Phys. 120, 5824 (2004).
W. Renz, M. Warner, Phys. Rev. Lett. 56, 1268 (1986).
H. Finkelmman, in Liquid Crystallinity in Polymers, edited by A. Ciferri (VCH Publishers Inc., New York, 1991).
A. Semenov, S. Vasilenko, Sov. Phys. JETP 63, 70 (1986).
D. Williams, G. Fredrickson, Macromolecules 25, 3561 (1992).
R. Holyst, M. Schick, J. Chem. Phys. 96, 730 (1992).
M.W. Matsen, C. Barrett, J. Chem. Phys. 109, 4108 (1998).
M. Reenders, G. ten Brinke, Macromolecules 35, 3266 (2002).
M. Motoyama, N. Yamazaki, M. Nonomura, T. Ohta, J. Phys. Soc. Jpn. 72, 991 (2003).
A. Shinozaki, D. Jasnow, A.C. Balazs, Macromolecules 27, 2496 (1994).
C. Vlahos, M. Kosmas, J. Phys. A: Math. Gen. 20, 1471 (1987).
R. Wang, Z. Jiang, J. Hu, Polymer 46, 6201 (2005).
S.V. Vasilenko, V. Shibaev, A.R. Khokhlov, Makromol. Chem. 186, 1951 (1985).
R. Matheson jr., P. Flory, Macromolecules 14, 954 (1981).
F. Auriemma, P. Corradini, M. Vacatello, J. Chem. Phys. 93, 8314 (1990).
X. Wang, M. Warner, J. Phys. A: Math. Gen. 20, 713 (1987).
A. ten Bosch, P. Maissa, P. Sixou, J. Chem. Phys. 79, 3462 (1983).
G.H. Fredrickson, V. Ganesan, F. Drolet, Macromolecules 35, 16 (2002).
A. Semenov, A. Subbotin, Sov. Phys. JETP 74, 660 (1992).
W. Maier, A. Saupe, Z. Naturforsch. A 15, 287 (1960).
M. Stephen, J. Straley, Rev. Mod. Phys. 46, 617 (1974).
A.M. Gupta, S.F. Edwards, J. Chem. Phys. 98, 1588 (1993).
A.J. Liu, G.H. Fredrickson, Macromolecules 26, 2817 (1993).
I. Teraoka, Polymer Solutions (Wiley, New York, 2002).
T.A. Vilgis, Phys. Rep. 336, 167 (2000).
P.G. de Gennes, Scaling Concepts in Polymer Physics (Cornell University Press, Ithaca and London, 1979).
C. Singh, M. Goulian, A. Liu, G. Fredrickson, Macromolecules 27, 2974 (1994).
P.G. de Gennes, J. Prost, The Physics of Liquid Crystals (Clarendon, Oxford, 1993).
H. Finkelmann, G. Rehage, Adv. Polym. Sci. 60, 99 (1984).
L. Noirez, C. Boeffel, A. Daoud-Aladine, Phys. Rev. Lett. 80, 1453 (1998).
L. Noirez, P. Keller, J. Cotton, Liq. Cryst. 18, 129 (1995).
L. Noirez, P. Davidson, W. Schwarz, G. Pepy, Liq. Cryst. 16, 1081 (1994).
E. Grulke, J. Brandrup, E. Immergut, Polymer Handbook (Wiley Interscience Publication, New York, 1998).
K. Almdal, M. Hillmyer, F. Bates, Macromolecules 35, 7685 (2002).
G. Fredrickson, A. Liu, F. Bates, Macromolecules 27, 2503 (1994).
A. Liu, G. Fredrickson, Macromolecules 25, 5551 (1992).
K. Lee, C. Han, Macromolecules 35, 3145 (2002).
R. Ivanova, R. Staneva, S. Geppert, B. Heck, B. Walter, W. Gronski, B. Stühn, Colloid Polym. Sci. 282, 810 (2004).
S.A. Brazovskii, Zh. Eksp. Teor. Fiz. 68, 175 (1975).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hernández-Jiménez, M., Westfahl jr., H. Theory of microphase separation on side-chain liquid-crystalline polymers with flexible spacers. Eur. Phys. J. E 23, 31–42 (2007). https://doi.org/10.1140/epje/i2006-10083-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1140/epje/i2006-10083-3