Abstract
Viscometric behavior of nearly equimolar block copolymers of the poly(methyl methacrylate)–polystyrene–poly(methacrylate) type are studied in various solvents. The behavior is discussed in relation to the incompatibility of the parent homopolymers in each solvent. A correlation is found between the excluded-volume interactions in the block copolymer chain and the incompatibility of the homopolymer pair. A high compatibility is observed for the pair in cyclohexanol, and this reinforces our previous argument that this solvent may provide a genuine θ condition for the block copolymer, wherein random-flight statistics prevails. In certain common solvents, the homopolymer pair is fairly compatible, and the viscometric behavior of the block copolymer shows no anomalies: the so-called phenomenon of intrachain phase separation is unlikely to be taking place in such solvents. In θ solvents for either one of the homopolymers, they become less compatible. Nevertheless in a θ solvent for polystyrene the block copolymer shows no anomalies. On the other hand, in θ solvents for poly(methyl methacrylate), significant anomalies are observed. The anomalies must be due to the triblock architecture of the block copolymer chains: the two poly(methyl methacrylate) side-chains undergo intrachain association, thereby restricting allowable conformations of the central polystyrene chain.
Similar content being viewed by others
Article PDF
References
T. Kotaka, H. Ohnuma, and Y. Murakami, J. Phys. Chem., 70, 4099 (1966).
H. Ohmura, T. Kotaka, and H. Inagaki, Polymer, 10, 501 (1969).
T. Kotaka, H. Ohnuma, and H. Inagaki, Polymer, 10, 517 (1969).
H. Ohnuma, Dissertation, Kyoto University, Kyoto, 1969.
W. H. Stockmayer, L. D. Moore, Jr., M. Fixman, and B. N. Epstein, J. Polym. Sci., 16, 517 (1955).
T. Kotaka, T. Tanaka, H. Ohnuma, Y. Murakami, and H. Inagaki, Polym. J., 1, 245 (1970).
A. Dobry and F. Boyer-Kawenoki, J. Polym. Sci., 2, 90 (1947).
R. L. Scott, J. Chem. Phys., 17, 268 (1949).
R. J. Kern and R. J. Solocombe, J. Polym. Sci., 15, 183 (1955).
G. M. Burnett, D. Meares, and C. Paton, Trans. Faraday Soc., 58, 737 (1962).
S. Krause, J. Phys. Chem., 68, 1948 (1964).
J. R. Urwin and J. M. Stearne, Makromol. Chem., 78, 197 (1964).
J. R. Urwin and J. M. Stearne, Makromol. Chem., 78, 204 (1964).
J. R. Urwin and J. M. Stearne, Eur. Polym. J., 1, 227 (1965).
H. Inagaki, Makromol. Chem., 86, 289 (1965).
H. Inagaki and T. Miyamoto, Makromol. Chem., 87, 166 (1965).
D. Froelich and H. Benoit, Makromol. Chem., 92, 224 (1966).
D. Froelich, J. Chim. Phys., 64, 1311 (1968).
See, for example, T. Inoue, T. Soen, H. Kawai, M. Fukatsu, and M. Kurata, J. Polym. Sci., Part B, 6, 75 (1968).
See, for example, S. Krause, Macromolecules, 3, 84 (1970).
M. Szwarc and A. Rembaum, J. Polym. Sci., 22, 189 (1956).
M. Szwarc, Fortschr. Hochpolym. Forsch., 2, 275 (1960).
M. Baer, J. Polym. Sci., Part A, 2, 417 (1964).
D. Freyss, P. Rempp, and H. Benoit, J. Polym. Sci., Part B, 2, 217 (1964).
T. Miyamoto and H. Inagaki, Polym. J., 1, 46 (1970).
See, for example, "Organic Solvents," J. A. Riddick, and E. E. Toops, Jr., Ed., Interscienc Publishers Inc., New York, N.Y., 1955.
H. Inagaki, H. Suzuki, M. Fujii, and T. Matsuo, J. Phys. Chem., 70, 1718 (1966).
T. Kotaka, Y. Murakami, and H. Inagaki, J. Phys. Chem., 72, 829 (1968).
T. Kotaka and N. Donkai, J. Polym. Sci., Part A-2, 6, 1745 (1968).
T. Kotaka, N. Donkai, and H. Inagaki, J. Polym. Sci., submitted.
W. Bushuk and H. Benoit, Compt. Rend., 244, 3167 (1958).
H. Benoit and C. Wippler, J. Chim. Phys., 57, 524 (1960).
See, for example, R. L. Baldwin and K. E. van Holde, Fortschr. Hochpolym. Forsch., 1, 451 (1960).
T. A. Orofino, J. Chem. Phys., 45, 4310 (1966).
G. V. Schulz, A. Haug, and R. Kirste, Z. Phys. Chem. (NF), 38, 1 (1963).
G. C. Berry, J. Chem. Phys., 44, 4550 (1966).
G. C. Berry, J. Chem. Phys., 46, 1338 (1967).
M. Kurata and W. H. Stockmayer, Fortschr. Hochpolym. Forsch., 3, 196 (1963).
W. H. Stockmayer and M. Fixman, J. Polym. Sci., Part C, 1, 137 (1963).
D. Berek, B. Bohmer, and D. Lath, Plast. Kautschuk, 14, 556 (1967).
See, for example P. J. Flory, "Statistical Mechanics of Chain Molecules," Interscience Publishers, New York, N.Y., 1969.
P. J. Flory, "Principles of Polymer Chemistry," Cornell University Press, Ithaca, N.Y., 1953.
See, for example, H. Inagaki, H. Suzuki, and M. Kurata, J. Polym. Sci., Part C, 15, 409 (1966).
J. M. G. Cowie, Polymer, 7, 387 (1966).
T. Norisuye, K. Kawahara, A. Teramoto, and H. Fujita, J. Chem. Phys., 49, 4330 (1968).
K. Kawahara, T. Norisue, and H. Fujita, J. Chem. Phys., 49, 4339 (1968).
G. Tanaka, S. Imai, and H. Yamakawa, J. Chem. Phys., 52, 2639 (1970).
C. W. Pyunn and M. Fixman, J. Chem. Phys., 42, 3838 (1965).
W. H. Stockmayer, Makromol. Chem., 35, 54 (1960).
Th. G. Scholte, J. Polym. Sci., Part A-2, 5, 461 (1967).
T. Tanaka and T. Kotaka, unpublished.
E. Teramoto, Busseiron Kenkyu, 39, 1 (1951).
E. Teramoto, Busseiron Kenkyu, 40, 18 (1951).
E. Teramoto, Busseiron Kenkyu, 41, 14 (1951).
E. Teramoto, Busseiron Kenkyu, 44, 36 (1951).
B. H. Zimm, W. H. Stockmayer, and M. Fixman, J. Chem. Phys., 21, 1716 (1953).
M. Fixman, J. Chem. Phys., 23, 1656 (1955).
L. A. Utracki, R. Simha, and L. J. Fetters, J. Polym. Sci., Part A-2, 6, 2051 (1968).
L. A. Utracki and R. Simha, Macromolecules, 1, 505 (1968).
T. Tanaka and T. Kotaka, unpublished experiments.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ohnuma, H., Kotaka, T. & Inagaki, H. Thermodynamic and Conformational Properties of Styrene–Methyl Methacrylate Block Copolymers in Dilute Solution. III. Viscometric Behavior in Relation to Incompatibility of Parent Homopolymers. Polym J 1, 716–726 (1970). https://doi.org/10.1295/polymj.1.716
Issue Date:
DOI: https://doi.org/10.1295/polymj.1.716