Light scattering and viscosity measurements were made on cyclohexane and toluene solutions of a series of polymacromonomer samples consisting of polystyrene with 65 monomer units in each side chain to determine the z-average mean-square radius of gyration ‹s2›z and the intrinsic viscosity [η] as functions of the weight average molecular weight in a range from 2.9×105 to 8.6×106. The theta temperature for the polymacromonomer in cyclohexane was determined to be 34.5°C. The ‹s2›z data in this solvent at 34.5°C and toluene at 15°C (a good solvent) were quantitatively described by the wormlike chain with λ−1 (the Kuhn segment length)=36 nm and ML (the molecular weight per unit contour length)=25000 nm−1 in the former and with λ−1=75 nm and ML=25000 nm−1 in the latter. The molecular weight dependence of [η] in each solvent was also explained by this model chain when the end effect arising from side chains near the main-chain ends was taken into account. The above λ−1 values in the two solvents and the previous estimates for polystyrene polymacromonomers with shorter side chains were used to examine the dependence of the backbone stiffness on side chain length. It was found that λ−1 increases almost linearly with the side-chain molecular weight for both solvents but with a larger slope in toluene than in cyclohexane.
K. Terao, Y. Takeo, M. Tazaki, Y. Nakamura, and T. Norisuye, Polym. J., 31, 193 (1999).
K. Terao, Y. Nakamura, and T. Norisuye, Macromolecules, 32, 711 (1999).
K. Terao, T. Hokajo, Y. Nakamura, and T. Norisuye, Macromolecules, 32, 3690 (1999).
K. Terao, S. Hayashi, Y. Nakamura, and T. Norisuye, Polym. Bull., 44, 309 (2000).
M. Wintermantel, M. Schmidt, Y. Tsukahara, K. Kajiwara, and S. Kohjiya, Macromol. Rapid Commun., 15, 279 (1994).
N. Nemoto, M. Nagai, A. Koike, and S. Okada, Macromolecules, 28, 3854 (1995).
M. Wintermantel, M. Gerle, K. Fischer, M. Schmidt, I. Wataoka, H. Urakawa, K. Kajiwara, and Y. Tsukahara, Macromolecules, 29, 978 (1996).
Y. Tsukahara, J. Inoue, Y. Ohta, S. Kohjiya, and Y. Okamoto, Polym. J., 26, 1013 (1994).
Gj Dezelic and J. Vavra, Croat. Chem. Acta, 38, 35 (1966).
M. L. Huggins, J. Am. Chem. Soc., 64, 2716 (1942).
D. F. Mead and R. M. Fuoss, J. Am. Chem. Soc., 64, 277 (1942).
F. W. Billmeyer, Jr., J. Polym. Sci., 4, 83 (1949).
Y. Tsukahara, S. Kohjiya, K. Tsutsumi, and Y. Okamoto, Macromolecules, 27, 1662 (1994).
H. Benoit and P. Doty, J. Phys. Chem., 57, 958 (1953).
H. Murakami, T. Norisuye, and H. Fujita, Macromolecules, 13, 345 (1980).
Y. Nakamura, Y. Wan, J. W. Mays, H. Iatrou, and N. Hadjichristidis, Macromolecules, 33, 8323 (2000).
correction for eq 6 appears in Macromolecules, 34, 2018 (2001).
T. Norisuye and H. Fujita, Polym. J., 14, 143 (1982).
T. Norisuye, Prog. Polym. Sci., 18, 543 (1993).
H. Yamakawa, “Helical Wormlike Chains in Polymer Solutions,” Springer-Verlag GmbH & Co., Berlin, 1997.
T. Yoshizaki, I. Nitta, and H. Yamakawa, Macromolecules, 21, 165 (1988).
Y. Nakamura, T. Norisuye, and A. Teramoto, Macromolecules, 24, 4904 (1991).
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Hokajo, T., Terao, K., Nakamura, Y. et al. Solution Properties of Polymacromonomers Consisting of Polystyrene V. Effect of Side Chain Length on Chain Stiffness. Polym J 33, 481–485 (2001). https://doi.org/10.1295/polymj.33.481
- Light Scattering
- Intrinsic Viscosity
- Polystyrene Polymacromonomer
- Wormlike Chain
- Chain Stiffness