[en] The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(?-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Hoffman theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX (where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-b-PCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.
R. S. Bezwada, D. D. Jamiolkowski and K. Cooper, in Handbook of Biodegradable Polymers, eds. A. J. Domb, J. Kost and D. M. Wiseman, Harwood, Singapore, 1997, ch. 2, pp. 29-61.
M. A. Sabino, J. Albuerne, A. J. Müller, J. Brisson and R. E. Prud'homme, Biomacromolecules, 2004 5, 358.
P. Rangarajan, R. A. Register and L. J. Fetters, Macromolecules, 1993, 26, 4640.
P. Rangarajan, R. A. Register, D. H. Adamson, L. J. Fetters, W. Bras, S. Naylor and A. J. Ryan, Macromolecules, 1995, 28, 1422.
A. J. Ryan, I. W. Hamley, W. Bras and F. S. Bates, Macromolecules, 1995, 28, 3860.
P. H. Richardson, R. W. Richards, D. J. Blundell, W. A. MacDonald and P. Mills, Polymer, 1995, 36, 3059.
D. J. Quiram, R. A. Register, G. R. Marchand and A. J. Ryan, Macromolecules, 1997, 30, 8338.
K. C. Douzinas, R. E. Cohen and A. F. Halasa, Macromolecules, 1991, 24, 4457.
I. W. Hamley, J. Patrick, A. Fairclough, N. J. Terrill, A. J. Ryan, P. M. Lipic, F. S. Bates and E. Towns-Andrews, Macromolecules, 1996, 29, 8835.
P. Rangarajan, R. A. Register, L. J. Fetters, W. Bras, S. Taylor and A. J. Ryan, Macromolecules, 1995, 28, 4932.
S. Nojima, K. Kato, S. Yamamoto and T. Ashida, Macromolecules, 1992, 25, 2237.
D. J. Quiram, R. A. Register, G. R. Marchand and A. J. Ryan, Macromolecules, 1997, 30, 4551.
A. Rohadi, R. Endo, S. Tanimoto, S. Sasaki and S. Nojima, Polym. Int., 2000, 32, 602.
A. Rohadi, S. Tanimoto, S. Sasaki and S. Nojima, Polym. J., 2000, 32, 859.
A. J. Ryan, J. P. A. Fairclough, I. W. Hamley, S.-M. Mai and C. Booth, Macromolecules, 1997, 30, 1723.
M. A. Hillmyer and F. S. Bates, Macromol. Symp., 1997, 117, 121.
Y.-L. Loo, R. A. Register and A. J. Ryan, Macromolecules, 2002, 35, 2365.
S. Nojima, M. Toei, S. Hara, S. Tanimoto and S. Sasaki, Polymer, 2002, 43, 4087.
G. Reiter, G. Castelein, J.-U. Sommer, A. Röttele and T. Thurn-Albrecht, Phys. Rev. Lett., 2001, 87, 226101.
C. Robitaille and J. Prud'homme, Macromolecules, 1983, 16, 665.
D. J. Quiram, R. A. Register, G. R. Marchand and D. H. Adamson, Macromolecules, 1998, 31, 4891.
M. Ueda, K. Sakurai, S. Okamoto, D. Lohse, W. J. MacKnight, S. Shinkai, S. Sakurai and S. Nomura, Polymer, 2003, 44, 6995.
G. Reiter, J. Polym. Sci.: Part B: Polym. Phys., 2003, 41, 1869.
Polymer Crystallization, Observations, Concepts and Interpretations, ed. J. U. Sommer and G. Reiter, Springer, Berlin, 2003.
A. J. Müller, V. Balsamo, M. L. Arnal, T. Jakob, H. Schmalz and V. Abetz, Macromolecules, 2002, 35, 3048.
M. L. Arnal, V. Balsamo, F. López-Carrasquero, J. Contreras, M. Carrillo, H. Schmalz, V. Abetz, E. Laredo and A. J. Müller, Macromolecules, 2001, 34, 7973.
G. Floudas and C. Tsitsilianis, Macromolecules, 1997, 30, 4381.
M. Gervais and B. Gallot, Polymer, 1981, 22, 1129.
B. Lotz and A. J. Kovacs, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1969, 10, 820.
J. J. J. O'Malley, Polym. Sci., Polym. Symp., 1977, 60, 151.
L. Zhu, Y. Chen, A. Zhang, B. H. Calhoun, M. Chun, R. P. Quirk, S. Z. D. Cheng, B. S. Hsiao, F. Yeh and T. Hashimoto, Phys. Rev. B, 1999, 60, 10022.
L. Zhu, S. Z. D. Cheng, B. H. Calhoun, Q. Ge, R. P. Quirk, E. L. Thomas, B. S. Hsiao, F. Yeh and B. Lotz, Polymer, 2001, 42, 5829.
L. Zhu, B. R. Mimnaugh, Q. Ge, R. P. Quirk, S. Z. D. Cheng, E. L. Thomas, B. Lotz, B. S. Hsiao, F. Yeh and L. Liu, Polymer, 2001, 42, 9121.
L. Zhu, S. Z. D. Cheng, P. Huang, Q. Ge, R. P. Quirk, E. L. Thomas, B. Lotz, B. S. Hsiao, F. Yeh and L. Liu, Adv. Mater., 2002, 14, 31.
L. Zhu, P. Huang, W. Y. Chen, Q Ge, R. P. Quirk, S. Z. D. Cheng, E. L. Thomas, B. Lotz, B. S. Hsiao, F. Yeh and L Liu, Macromolecules, 2002, 35, 3553.
J. T. Xu, J. J. Yuan and S. Y. Cheng, Eur. Polym. J., 2003, 39, 2091.
P. A. Weimann, D. A. Hajduk, C. Chu, K. A. Chaffin, J. C. Brodil and F. S. Bates, J. Polym. Sci.: Part B: Polym. Phys., 1999, 37, 2053.
Y. L. Loo, R. A. Register, A. J. Ryan and G. T. Dee, Macromolecules, 2001, 34, 8968.
Y. K. Choi, Y. H. Bae and S. W. Kim, Macromolecules, 1998, 31, 8766.
B. Bogdanov, A. Vidts and H. Berghmans, Macromolecules, 1999, 32, 726.
Y. Wang and M. Hillmyer, J. Polym. Sci.: Part A: Polym. Chem., 2001, 39, 2755.
J. Albuerne, L. Márquez, A. J. Müller, J. M. Raquez, Ph. Degée, Ph. Dubois, V. Castelletto and I. W. Hamley, Macromolecules, 2003, 36, 1633.
R. M. Ho, P. Y. Hsieh, W. H. Tseng, C. C. Lin, B. H. Huang and B. Lotz, Macromolecules, 2003, 36, 9085.
A. J. Müller, J. Albuerne, L. M. Esteves, L. Márquez, J. M. Raquez, Ph. Degée, Ph. Dubois, S. Collins and I. W. Hamley, Macromolecular Symp., 2004, in press.
N. Bhattarai, H. Y. Kim, D. I. Cha, D. R. Lee and D. I. Yoo, Eur. Polym. J., 2003, 39, 1365.
J.-M. Raquez, P. Degée, R. Narayan and P. Dubois, Macromol. Rapid Commun., 2000, 21, 1063.
A. Lendlein and L. Langer, Science, 2002, 296, 1673.
J. K. Hobbs, A. D. L. Humphris and M. J. Miles, Macromolecules, 2001, 34, 5508.
B. Fillon, J. C. Wittmann, B. Lotz and A. Thierry, J. Polym. Sci., Part B: Polym. Phys., 1993, 31, 1383.
V. Castillo, A. J. Müller and M. Hillmyer, 2004, unpublished results.
M. A. Sabino, J. L. Feijoo and A. J. Müller, Macromol. Chem. Phys., 2000, 201, 2687.
J. I. Lauritzen Jr. and J. D. Hoffman, J. Appl. Phys., 1973, 44, 4340.
Physical Properties of Polymers Handbook, ed. J. E. Mark, AIP Press, New York, 1996.
J. Schultz, Polymer Crystallization, American Chemical Society, Washington, 2001.
S. Andjelic, D. Jamiolkowski, J. Mcdivitt, J. Fischer, J. Zhou and R. Vetrecin, J. Appl. Polym. Sci., 2001, 79, 742.
M. Avrami, J. Chem. Phys., 1939, 7, 1103; M. Avrami, J. Chem. Phys., 1940, 8, 212; M. Avrami, J. Chem. Phys., 1941, 9, 177.
M. Avrami, J. Chem. Phys., 1939, 7, 1103; M. Avrami, J. Chem. Phys., 1940, 8, 212; M. Avrami, J. Chem. Phys., 1941, 9, 177.
M. Avrami, J. Chem. Phys., 1939, 7, 1103; M. Avrami, J. Chem. Phys., 1940, 8, 212; M. Avrami, J. Chem. Phys., 1941, 9, 177.
L. Mandelkern, in The Crystalline State, eds. J. E. Mark, A. Eisenberg, W. W. Graessley, L. Mandelkern and J. L. Koenig, Physical Properties of Polymers, 2nd edn., ACS, Washington, 1993.
W. S. Lambert and P. J. Phillips, Macromolecules, 1994, 27, 3537.
V. Balsamo, Y. Paolini, G. Ronca and A. J. Müller, Macromol. Chem. Phys., 2000, 201, 2711.
H. Schmalz, A. J. Müller and V. Abetz, Macromol. Chem. Phys., 2003, 204, 111.
M. L. Arnal, F. López-Carrasquero, E. Laredo and A. J. Müller, Eur. Polym. J., 2004, 40, 1461.
B. Wunderlich, Macromolecular Physics, Volume 2, Crystal Nucleation, Growth, Annealing, Academia Press, New York, 1976, pp. 52-70.
Polymer Handbook, ed. J. Brandrup, E. H. Immergut, E. A. Grulke, A. Abe and D. R. Bloch, 4th edn., John Wiley and Sons, New York, 1999.
T. Shiomi, H. Takeshita, H. Kawaguchi, M. Nagai, K. Takenaka and M. Miya, Macromolecules, 2002 35, 8056.
