Abstract
Second and third virial coefficients (A2 and A3, respectively) for cyclohexane solutions (34.5 °C) of three four-arm star polystyrene (PS) samples with a benzyl group at each arm end (4SPS-Bz) and two four-arm star PS samples with a sec-butyl group at each arm end (4SPS-Bu) were determined as functions of weight-average molecular weight Mw lower than 1:5 × 104. As in the case for linear PS with benzyl ends, A2 for 4SPS-Bz at the theta temperature (34.5 °C), where A2 vanishes for sufficiently high Mw, was negative and decreased with lowering Mw in contrast to the increase of positive A2 for 4SPS-Bu. The negative A2 for 4SPS-Bz was ascribed to the effects of three-segment interactions and binary interactions between middle and junction point segments, while the positive A2 for 4SPS-Bu was explained as due to the effects from arm ends. These findings reveal that the previously observed lowering in apparent theta temperature (with decreasing Mw), where A2 = 0 for a given Mw, for four-arm star polystyrene is attributed to the arm-end effect. The values of A3 for both 4SPS-Bz and 4SPS-Bu were positive and increased with decreasing Mw at the theta temperature, showing significant three-segment interactions among two middle and one junction point or one arm-end segment.
Similar content being viewed by others
Article PDF
References
T. Mizuno, K. Terao, Y. Nakamura, and T. Norisuye, Macro-molecules, 38, 4432 (2005).
K. Huber and W. H. Stockmayer, Macromolecules, 20, 1400 (1987).
Y. Einaga, F. Abe, and H. Yamakawa, Macromolecules, 26, 6243 (1993).
H. Yamakawa, Macromolecules, 25, 1912 (1992).
J.-C. Meunier and R. Van Leemput, Makromol. Chem., 147, 191 (1971).
G. C. Berry, J. Polym. Sci., A-2, 9, 687 (1971).
J.-G. Zilliox, Makromol. Chem., 156, 121 (1972).
F. Candau, C. Strazielle, and H. Benoit, Makromol. Chem., 170, 165 (1973).
J. E. L. Roovers and S. Bywater, Macromolecules, 7, 443 (1974).
N. Khasat, R. W. Pennisi, N. Hadjichristidis, and L. J. Fetters, Macromolecules, 21, 1100 (1988).
B. J. Bauer, L. J. Fetters, W. W. Graessley, N. Hadjichristidis, and G. F. Quack, Macromolecules, 22, 2337 (1989).
F. Candau, P. Rempp, and H. Benoit, Macromolecules, 5, 627 (1972).
B. J. Bauer, N. Hadjichristidis, L. J. Fetters, and J. E. L. Roovers, J. Am. Chem. Soc., 102, 2410 (1980).
B. J. Cherayil, J. F. Douglas, and K. F. Freed, J. Chem. Phys., 87, 3089 (1987).
M. Okumoto, K. Terao, Y. Nakamura, T. Norisuye, and A. Teramoto, Macromolecules, 30, 7493 (1997).
T. Altares, D. P. Wyman, V. R. Allen, and K. Meyersen, J. Polym. Sci., Part A: Polym. Chem., 3, 4131 (1965).
D. J. Worsfold, J.-G. Zilliox, and P. Rempp, Can. J. Chem., 47, 3379 (1969).
J.-C. Meunier and R. Van Leemput, Makromol. Chem., 142, 1 (1971).
J. E. L. Roovers and S. Bywater, Macromolecules, 5, 384 (1972).
R. W. Pennisi and L. J. Fetters, Macromolecules, 21, 1094 (1988).
G. Deželić and J. Vavra . Chem. Acta, 38, 35 (1966).
Y. Einaga, F. Abe, and H. Yamakawa, J. Phys. Chem., 96, 3948 (1992).
G. C. Berry, J. Chem. Phys., 44, 4550 (1966).
C. E. H. Bawn, F. J. Freeman, and A. R. Kamaliddin, Trans. Faraday Soc., 46, 862 (1950).
T. Sato, T. Norisuye, and H. Fujita, J. Polym. Sci., Part B: Polym. 25, 1 (1987).
Y. Miyaki, Y. Einaga, and H. Fujita, Macromolecules, 11, 1180 (1978).
Y. Nakamura, T. Norisuye, and A. Teramoto, Macromolecules, 24, 4904 (1991).
H. Yamakawa and T. Yoshizaki, J. Chem. Phys., 119, 1257 (2003).
B. H. Zimm, J. Chem. Phys., 14, 164 (1946).
H. Yamakawa, F. Abe, and Y. Einaga, Macromolecules, 27, 3272 (1994).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nishi, Y., Nakamura, Y. & Norisuye, T. Effects of Chain Ends and Three-Segment Interactions on Second and Third Virial Coefficients of Four-Arm Star Polystyrenes. Polym J 41, 58–62 (2009). https://doi.org/10.1295/polymj.PJ2008183
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2008183
Keywords
This article is cited by
-
Second and third virial coefficients of low-molecular-weight polyisoprene in 1,4-dioxane
Polymer Journal (2014)
-
Effects of side-chain ends on the stiffness and excluded-volume parameters of polymacromonomers
Polymer Journal (2012)