Abstract
The morphology and melting behavior of poly(ε-caprolactone)-block-polystyrene (PCL-b-PS) copolymers, quenched from the melt or cast from the toluene solution, were investigated by small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) as a function of copolymer composition. The glass transition temperature of PS blocks is higher than the melting temperature of PCL blocks, Tm,PCL, in this system, so that the molecular motion is extremely restricted when the PCL block crystallizes in temperatures below Tm,PCL. DSC results showed that the quenched PCL-b-PS did not crystallize at any temperature when PCL vol%, φPCL, was less than 26%, whereas it crystallized partially when φPCL≥34% and the crystallinity increased with increasing φPCL, suggesting that φPCL affects significantly the crystallizability of PCL blocks. However, crystallization was observed for all PCL-b-PS copolymers cast at 20°C, and the crystallinity decreased appreciably with increasing the casting temperature. SAXS results revealed that high crystallinity PCL-b-PS copolymers had an intensity peak arising from the lamellar morphology, an alternating structure consisting of crystalline lamellae and amorphous layers, whereas low crystallinity PCL-b-PS copolymers did not show any SAXS peak, indicating the morphological difference among crystallized PCL-b-PS copolymers. The morphology formed in PCL-b-PS is discussed as a function of φPCL in terms of the lamellar morphology observed for crystalline homopolymers.
Similar content being viewed by others
Article PDF
References
R. Unger, D. Beyer, and E. Donth, Polymer, 32, 3305 (1991).
S. Nojima, K. Kato, S. Yamamoto, and T. Ashida, Macromolecules, 25, 2237 (1992).
P. Rangarajan, R. A. Register, and L. J. Fetters, Macromolecules, 26, 4640 (1993).
S. Nojima, H. Nakano, and T. Ashida, Polym. Commun., 34, 4168 (1993).
S. Nojima, H. Nakano, Y. Takahashi, and T. Ashida, Polymer, 35, 3479 (1994).
P. Rangarajan, R. A. Register, D. H. Adamson, L. J. Fetters, W. Bras, S. Naylor, and A. J. Ryan, Macromolecules, 28, 1422 (1995).
A. J. Ryan, I. W. Hamley, W. Bras, and F. S. Bates, Macromolecules, 28, 3860 (1995).
S. Nojima, S. Yamamoto, and T. Ashida, Polym. J., 27, 673 (1995).
Z. Gan, B. Jiang, and J. Zhang, J. Appl. Polym. Sci., 59, 961 (1996).
S. M. Mai, J. P. A. Fairclough, K. Viras, P. A. Gorry, I. W. Hamley, A. J. Ryan, and C. Booth, Macromolecules, 30, 8392 (1997).
E. A. DiMarzio, C. M. Guttman, and J. D. Hoffman, Macromolecules, 13, 1194 (1980).
M. D. Whitmore and J. Noolandi, Macromolecules, 21, 1482 (1988).
K. C. Douzinas and R. E. Cohen, Macromolecules, 25, 5030 (1992).
I. W. Hamley, J. P. A. Fairclough, A. J. Ryan, F. S. Bates, and E. T. Andrews, Polym. Commun., 37, 4425 (1996).
D. J. Quiram, R. A. Register, and G. R. Marchand, Macromolecules, 30, 4551 (1997).
S. Nojima, K. Hashizume, A. Rohadi, and S. Sasaki, Polymer, 38, 2711 (1997).
M. Gervais and B. Gallot, Makromol. Chem., 178, 1577 (1977).
M. Gervais and B. Gallot, Makromol. Chem., 171, 157 (1973).
M. Gervais and B. Gallot, Polymer, 22, 1129 (1981).
M. Gervais, B. Gallot, R. Jerome, and P. Teyssie, Makromol. Chem., 182, 989 (1981).
J. J. Herman, R. Jerome, P. Teyssie, M. Gervais, and B. Gallot, Makromol. Chem., 179, 1111 (1978).
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).
L. Liu, H. Li, B. Jiang, and E. Zhou, Polymer, 35, 5511 (1994).
V. Balsamo, F. Gyldenfeldt, and R. Stadler, Macromol. Chem. Phys., 197, 3317 (1996).
L. Liu, B. Jiang, and E. Zhou, Polymer, 37, 3937 (1996).
L. Liu, F. Yeh, and B. Chu, Macromolecules, 29, 5336 (1996).
S. Nojima, H. Tanaka, A. Rohadi, and S. Sasaki, Polymer, 39, 1727 (1998).
S. Nojima, Y. Terashima, and T. Ashida, Polymer, 27, 1007 (1986).
H. Tanaka and T. Nishi, Phys. Rev. A, 39, 783 (1989).
S. Nojima, K. Satoh, and T. Ashida, Macromolecules, 24, 942 (1991).
V. Crescenzi, G. Manzini, G. Galzolari, and C. Borri, Eur. Polym. J., 8, 449 (1972).
M. J. Richardson and N. G. Savil, Polymer, 18, 3 (1977).
K. Ito and Y. Yamashita, Macromolecules, 11, 68 (1978).
L. Mandelkern, “Crystallization of Polymers,” McGraw-Hill, New York, N.Y., 1964.
B. Wunderlich, “Macromolecular Physics 3,” Academic Press, New York, N.Y., 1980.
P. J. Phillips, G. J. Rensch, and K. D. Taylor, J. Polym. Sci., B25, 1725 (1987).
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).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Nojima, S., Fujimoto, M., Kakihira, H. et al. Effects of Copolymer Composition on the Crystallization and Morphology of Poly(ε-caprolactone)-block-Polystyrene. Polym J 30, 968–975 (1998). https://doi.org/10.1295/polymj.30.968
Issue Date:
DOI: https://doi.org/10.1295/polymj.30.968
Keywords
This article is cited by
-
Regioselective synthesis of cellulosic janus bottlebrushes with polystyrene and poly (ε-caprolactone) side chains and their solid-state microphase separation
Cellulose (2021)
-
Preparation of long-range ordered nanostructures in semicrystalline diblock copolymer thin films using micromolding
Chinese Journal of Polymer Science (2014)