Abstract
The morphology formed in poly(ε-caprolactone)-block-polybutadiene (PCL-b-PB) copolymers by casting the toluene solution was investigated by small-angle X-Ray scattering (SAXS) and differential scanning calorimetry (DSC) as a function of total molecular weight Mn and crystallization temperature Tc, and compared with the morphology formed by quenching from the microphase-separated melt. The lamellar morphology was observed at any Tc in the solution-cast PCL-b-PB with lower Mn (Mn≤30000), and the repeating distance of this morphology was little affected by Tc while it increased significantly with increasing Tc for the quenched PCL-b-PB. The solution-cast PCL-b-PB with higher Mn (Mn≥44000) had the lamellar morphology or crystallized microdomain structure (i.e., a microdomain structure in which the PCL block partially crystallized) depending on Tc though the crystallized microdomain structure was always observed in the quenched samples. The PCL crystallinity χc (i.e., the weight fraction of crystallized PCL blocks against total PCL blocks in the system) was 0.63—0.79 in the lamellar morphology while it was considerably low in the crystallized microdomain structure (χc<0.23), suggesting the substantial difficulty of crystallization within the curved microdomain. The mechanism of morphology formation in the solution-cast samples is discussed by considering the competition between microphase separation and crystallization during the solvent evaporation at each Tc and Mn.
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References
I. W. Hamley, “The Physics of Block Copolymers”, Oxford University Press, Oxford, 1998.
E. A. DiMarzio, C. M. Guttman, and J. D. Hoffman, Macromolecules, 13, 1194 (1980).
M. D. Whitmore and J. Noolandi, Macromolecules, 21, 1482 (1988).
S. Nojima, K. Kato, S. Yamamoto, and T. Ashida, Macromolecules, 25, 2237 (1992).
S. Nojima, S. Yamamoto, and T. Ashida, Polym. J., 27, 673 (1995).
D. J. Quiram, R. A. Register, and G. R. Marchand, Macromolecules, 30, 4551 (1997).
I. W. Hamley, J. P.A. Fairclough, F. S. Bates, and A. J. Ryan, Polymer, 39, 1429 (1998).
E. Hirata, T. Ijitsu, T. Soen, T. Hashimoto, and H. Kawai, Polymer, 16, 249 (1975).
M. Gervais and B. Gallot, Makromol. Chem., 178, 2071 (1977).
J. J. Herman, R. Jerome, P. Teyssie, M. Gervais, and B. Gallot, Makromol. Chem., 182, 997 (1981).
J. Heuschen, R. Jerome, and P. Teyssie, J. Polym. Sci., B27, 523 (1989).
K. C. Douzinas, R. E. Cohen, and A. F. Halasa, Macromolecules, 24, 4457 (1991).
R. Unger, D. Beyer, and E. Donth, Polymer, 32, 3305 (1991).
K. C. Douzinas and R. E. Cohen, Macromolecules, 25, 5030 (1992).
A. J. Lovinger, B. J. Han, F. J. Padden, and P. A. Mirau, J. Polym. Sci., B31, 115 (1993).
S. Ishikawa, S. Sasaki, and T. Fukutomi, J. Appl. Polym. Sci., 48, 509 (1993).
L. Liu, B. Jiang, and E. Zhou, Polymer, 37, 3937 (1996).
A. Rohadi, R. Endo, S. Tanimoto, S. Sasaki, and S. Nojima, Polym. J., 32, 602 (2000).
S. Nojima, D. Wang, and T. Ashida, Polym. J., 23, 1473 (1991).
S. Nojima, H. Nakano, Y. Takahashi, and T. Ashida, Polymer, 35, 3479 (1994).
S. Nojima, K. Hashizume, A. Rohadi, and S. Sasaki, Polymer, 38, 2711 (1997).
S. Nojima, M. Kuroda, and S. Sasaki, Polym. J., 29, 642 (1997).
S. Nojima, H. Tanaka, A. Rohadi, and S. Sasaki, Polymer, 39, 1727 (1998).
V. Crescenzi, G. Manzini, G. Galzolari, and C. Borri, Eur. Polym. J., 8, 449 (1972).
I. W. Hamley, J. P.A. Fairclough, N. J. Terrill, A. J. Ryan, P. M. Lipic, F. S. Bates, and E. T. Andrews, Macromolecules, 29, 8835 (1996).
A. J. Ryan, J. P.A. Fairclough, I. W. Hamley, S. M. Mai, and C. Booth, Macromolecules, 30, 1723 (1997).
N. Sakamoto and T. Hashimoto, Macromolecules, 28, 6825 (1995).
S. Nojima, S. Hara, S. Tanimoto, and S. Sasaki, manuscript in preparation.
L. Leibler, Macromolecules, 13, 1602 (1980).
S. Sakurai, Trends in Polym. Sci., 3, 90 (1995).
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Rohadi, A., Tanimoto, S., Sasaki, S. et al. Morphological Difference between Solution-Cast and Melt-Quenched Crystalline-Amorphous Diblock Copolymers. Polym J 32, 859–865 (2000). https://doi.org/10.1295/polymj.32.859
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DOI: https://doi.org/10.1295/polymj.32.859