Abstract
The effect of the structure of copolymers (random, alternate or diblock) on their dynamics has been studied by dielectric spectroscopy. Six copolymers of styrene and methyl methacrylate (three diblocks, one alternate and two random) have been studied. The results show that the sub- T g transitions of the diblock samples can be described by one asymmetric Havriliak-Negami (HN) function, while two are necessary for the rest of the copolymers (β and γ relaxations). The characteristic times of the sub- T g relaxations show an Arrhenius temperature dependence and there is a strong coupling of the α and β relaxations at high temperatures. The deconvolution of the merging relaxations has been made in the framework of the Williams Ansatz set out in terms of Havriliak-Negami distributions. Because the 2D 2H-NMR results excluded any significant contribution from the rotation of the methoxy group of the methacrylate group around the C-OCH3 bond, the γ relaxation may be assigned to the rotation of the methyl methacrylate group in a styrene-rich environment. The Molecular Dynamics simulations of a poly(methyl methacrylate) homopolymer and of the alternate copolymer are in qualitative agreement with the experimental results, although they predict smaller values for the activation energy of the sub- T g relaxations.
Similar content being viewed by others
References
D.R. Paul, C.B. Bucknall (Editors), Polymer Blends, Vol. 1 (Wiley, New York, 2000).
I.W. Hamley, The Physics of Block Copolymers (Oxford University Press, Oxford, 1998).
J.M.G. Cowie, Polymers: Chemistry and Physics of Modern Materials, 2nd edition (Chapman and Hall, London, 1991).
T. Kokata, K. Adachi, Macromol. Symp. 3, 124 (1997).
I. Alig, F. Kremer, G. Fytas, J. Roovers, Macromolecules 25, 5277 (1992).
K. Karatasos, S.H. Anastasiadis, G. Floudas, G. Fytas, S. Pispas, H. Hadjichristidis, T. Pakula, Macromolecules 29, 1326 (1996).
A. Kyritsis, P. Pisis, S.-M. Mai, C. Booth, Macromolecules 33, 4581 (2000).
S. Moreno, R.G. Rubio, Macromolecules 35, 5483 (2002).
L. Ma, Ch. He, T. Suzuki, M. Azuma, Y. Bin, H. Kurosu, M. Matsuo, Macromolecules 36, 8056 (2003).
M. Encinar, E. Guzmán, M.G. Prolongo, R.G. Rubio, C. Sandoval, F. Gonzalez-Nilo, L. Gargallo, D. Radic, Polymer 49, 168 (2008).
A. Zetsche, E.W. Fischer, Acta. Polym. 45, 168 (1994).
A. Sanchis, M.G. Prolongo, R.M. Masegosa, R.G. Rubio, Macromolecules 28, 2693 (1995).
M. Wübbenhorst, V. Lupascu, Proc. ISE-12 (2005), DOI:10.1109/ISE.2005.1612325.
O. Van den Berg, M. Wübbenhorst, S.J. Picken, W.F. Jager, J. Non-Cryst. Solids 351, 2694 (2005).
A-V.G. Ruzette, P. Banerjee, A.M. Mayes, M. Pollard, T.P. Russell, R. Jerome, S.R. Hjelm, P. Thiyarajan, Macromolecules 31, 8509 (1998).
T.P. Russell, R.P. Hjelm, P.A. Seeger, Macromolecules 23, 890 (1990).
T.E. Karis, T.P. Russell, Y. Gallot, A.M. Mayes, Macromolecules 28, 1129 (1995).
H. Ahn, D.Y. Ryu, Y. Kim, K.W. Kwon, J. Lee, J. Cho, Macromolecules 42, 7897 (2009).
V. Lupascu, S.J. Picken, M. Wübbenhorst, J. Non-Cryst. Solids 352, 5594 (2006).
R. Bergman, F. Alvarez, A. Alegría, J. Colmenero, J. Non-Cryst. Solids 235-238, 580 (1998).
A. Arbe, A-C. Genix, J. Colmenero, D. Richter, P. Fouquet, Soft Matter 4, 1792 (2008).
K. Schmidt-Rohr, A.S. Kulik, H.W. Beckhan, A. Ohlemacher, U Pawelzik, C. Boeffel, H.W. Spiess, Macromolecules 27, 4733 (1994).
J.F. de Dens, G.P. Souza, W.A. Corradini, T.D.Z. Atvars, L. Akcelrud, Macromolecules 38, 6938 (2004).
M. Vacatello, P.J. Flory, Macromolecules 19, 405 (1986).
V. Morais, M. Encinar, M.G. Prolongo, R.G. Rubio, Polymer 47, 2349 (2006).
T. Pakula, G. Floudas, in Block Copolymers, edited by F. Baltá-Calleja, Z. Roslaniec (Marcel Dekker, New York, 2000).
S. Theobald, W. Pechold, B. Stoll, Polymer 42, 289 (2001).
R. Bergman, F. Alvarez, A. Alegría, J. Colmenero, J. Chem. Phys. 109, 7546 (1998).
D. Gómez, A. Alegría, A. Arbe, J. Colmenero, Macromolecules 34, 503 (2001).
G. Domínguez-Espinosa, D. Ginestar, M.J. Sanchís, R. Díaz Calleja, E. Riande, J. Chem. Phys. 129, 104513 (2008).
G. Williams, C.D. Watts, in NMR. Basic Principles and Progress edited by P. Diehl, E. Fluck, H. Gunther, J.B. Robert, Vol. 4 (Springer-Verlag, Berlin, 1971).
M.G. Prolongo, C. Salom, R.M. Masegosa, S. Moreno, R.G. Rubio, Polymer 38, 5097 (1997).
H. Sun, S.J. Mumby, J.R. Maple, A.T. Hagler, J. Am. Chem. Soc. 116, 2978 (1994).
E. Saiz, J.P. Hummel, P.J. Flory, M. Plavsic, J. Phys. Chem. 85, 3211 (1981).
S. Havriliak jr, S.J. Havriliak, Dielectric and Mechanical Relaxation in Materials: Analysis, Interpretation, and Application to Polymers, chapt. 1 (Hanser Verlag, New York, 1997).
J. Weese, Comput. Phys. Commun. 77, 429 (1993).
S. Moreno, R.G. Rubio, G. Luengo, F. Ortega, M.G. Prolongo, Eur. Phys. J. E 4, 173 (2001).
R. Zorn, J. Polym. Sci., Polym. Phys. B 38, 1043 (1999).
E. Schlosser, A. Schönhals, Colloid Polym. Sci. 267, 963 (1989).
E. Riande, R. Díaz-Calleja, Electrical Properties of Polymers, chapt. 4 (Marcel Dekker, New York, 2004).
K.L. Ngai, M. Paluch, J. Chem. Phys. 120, 857 (2004).
S. Mashimo, S. Yagihara, Y. Iwasa, J. Polym. Sci., Polym. Phys. Ed. 16, 1761 (1978).
C.A. Angell, Science 267, 1924 (1995).
K.L. Ngai, Macromolecules 32, 7140 (1999).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Encinar, M., Prolongo, M.G., Rubio, R.G. et al. Dielectric and molecular dynamics study of the secondary relaxations of poly(styrene-co-methylmethacrylate) copolymers: Influence of the molecular architecture. Eur. Phys. J. E 34, 134 (2011). https://doi.org/10.1140/epje/i2011-11134-4
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1140/epje/i2011-11134-4