[en] Conditions of the living homopolymerization of epsilon-caprolactone (CL), lactides (LA), and of the homo-oligomerization of gamma-butyrolactone (BL) are briefly described. Then block and random copolymerizations of CL with LA are shortly reviewed. The microstructure of the resulting copolyesters in relation to some peculiarities of these processes is discussed in more detail. It is also shown that the otherwise 'non-polymerizable' BL does form high molecular weight copolymers with CL, containing up to 50 mol% repeating units derived from BL. Their molecular weight is controlled by the concentrations of the consumed comonomers and the starting concentration of the initiator. NMR and DSC data indicate the random structure of copolymers. TGA traces of the BL/CL copolymers show that the presence of the gamma-oxybutyryl repeating units randomly distributed within the poly(CL) chains improves the thermal stability of the latter.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Duda, Andrzej; Polish Academy of Sciences, Lodz, Poland > Department of Polymer Chemistry > Center of Molecular and Macromolecular Studies
Biela, Tadeusz; Polish Academy of Sciences, Lodz, Poland > Department of Polymer Chemistry > Center of Molecular and Macromolecular Studies
Libiszowski, Jan; Polish Academy of Sciences, Lodz, Poland > Department of Polymer Chemistry > Center of Molecular and Macromolecular Studies
Penczek, Stanislaw; Polish Academy of Sciences, Lodz, Poland > Department of Polymer Chemistry > Center of Molecular and Macromolecular Studies
Dubois, Philippe; Université de Liège - ULiège and University of Mons-Hainaut (UMH) > Department of Chemistry (Liège) > Center for Education and Research on Macromolecules (CERM, Liège), Laboratory of Polymeric and Composite Materials (SMPC, Mons)
Mecerreyes, David; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Huang, S.J., Biodegradable Polymers, in Encyclopedia of Polymer Science and Engineering, Vol. 2, ed. H. F. Mark et al. J. Wiley and Sons, Inc., New York, 1985, p. 220.
Pitt, C.G., Poly-ε-caprolactone and its copolymers, in Biodegradable Polymers as Drug Delivery Systems, ed. M. Chasin and R. Langer. Marcel Dekker, Inc., New York, 1990, p. 71.
Vanhoorne, P., Dubois, Ph., Jérôme, R. and Teyssié, Ph., Macromolecules, 1992, 25, 37.
Van Natta, F. J., Hill, J. W. and Carothers, W. H., J. Am. Chem. Soc., 1934, 56, 455.
Hofman, A., Slomkowski, S. and Penczek, S., Makromol. Chem. Rapid Commun., 1987, 8, 387.
Endo, M., Aida, T. and Inoue, S., Macromolecules, 1987, 20, 2982.
Kricheldorf, H. R., Berl, M. and Scharnagl, N., Macromolecules, 1988, 21, 286.
Duda, A., Florjanczyk, Z., Hofman, A., Slomkowski, S. and Penczek, S., Macromolecules, 1990, 23, 1640.
Dubois, Ph., Jérôme, R. and Teyssié, Ph., Polym. Bull. (Berlin), 1989, 22, 475.
Duda, A. and Penczek, S., Macromol. Rapid Commun., 1995, 16, 67.
Duda, A. and Penczek, S., Macromolecules, 1995, 28, 5981.
Ropson, N., Dubois, Ph., Jérôme, R. and Teyssiè, Ph., Macromolecules, 1995, 28, 7589.
Stevels, W. M., Ankoné, M. J. K., Dijkstra, P. J. and Feijen, J., Macromolecules, 1996, 29, 8296.
Penczek, S. and Duda, A., Macromol. Symp., 1996, 107, 1.
Vert, M., Li, S.M., Spenlehauer, G. and Guérin, J., J. Mater. Sci. Mater. Med., 1992, 3, 342.
Kharash, G.B., Sanchez-Riera, F. and Severson, D.K., Polymers of lactid acid, in Plastics from Microbes, ed. D. P. Mobley. Hanser Publishers, Munich, New York, 1994, p. 93.
Carothers, W. H., Dorough, G. and Van Natta, F., J. Am. Chem. Soc., 1932, 54, 761.
Dubois, Ph., Jacobs, C., Jérôme, R. and Teyssié, Ph., Macromolecules, 1991, 24, 2266.
Degée, Ph., Dubois, Ph. and Jérôme, R., Macromol. Symp., 1997, 123, 65.
Degée, Ph., Dubois, Ph. and Jérôme, R., Macromol. Chem. Phys., 1997, 198, 1973.
Baran, J., Duda, A., Kowalski, A., Szymanski, R. and Penczek, S., Macromol. Symp., 1997, 123, 93.
Baran, J., Duda, A., Kowalski, A., Szymanski, R. and Penczek, S., Macromol. Rapid Commun., 1997, 18, 325.
Stevels, W. M., Ankoné, M. J. K., Dijkstra, P. J. and Feijen, J., Macromolecules, 1996, 29, 6132.
Kricheldorf, H. R., Kreiser-Saunders, I. and Boettcher, C., Polymer, 1995, 36, 1253.
Montaudo, G., Montaudo, M. S., Puglisi, C., Samperi, F., Spassky, N., Le Borgne, A. and Wisniewski, M., Macromolecules, 1996, 29, 6461.
Duda, A. and Penczek, S., Macromolecules, 1990, 23, 1636.
Odian, G., in Principles of Polymerization, 3rd edition. Wiley-Interscience, New York, 1991, p. 570.
Tada, K., Numata, Y., Saegusa, T. and Furukawa, J., Makromol. Chem., 1964, 77, 220.
Kricheldorf, H. R., Mang, T. and Jonté, J. M., Makromol. Chem., 1985, 186, 955.
Fukuzaki, H., Aika, Y., Yoshida, M., Asano, M. and Kumakura, M., Makromol. Chem., 1989, 190, 1553.
Hori, Y., Yamaguchi, A. and Hagiwara, T., Polymer, 1995, 36, 4703.
Duda, A., Penczek, S., Dubois, Ph., Mecerreyes, D. and Jérôme, R., Macromol. Chem. Phys., 1996, 197, 1273.
Lebedev, B. V., Evstropov, A. A., Lebedev, N. K., Karpova, E. A., Ludvig, E. B. and Beleynkaya, B. G., Vysokomol. Soedin. Ser. A., 1978, 20, 1974.
Evstropov, A. A., Lebedev, B. V., Kiparisova, E. G., Alekseev, V. A. and Stashina, G. A., Vysokomol. Soedin. Ser. A., 1980, 22, 2450.
Korte, F. and Glet, H., J. Polym. Sci. Part C., 1966, 4, 685.
Biela, T., Duda, A., Penczek, S., Dubois, Ph., Mecerreyes, D. and Jérôme, R., in preparation.
Jacobs, C., Dubois, Ph., Jérôme, R. and Teyssiè, Ph., Macromolecules, 1991, 24, 3027.
Kowalski, A., Libiszowski, J., Duda, A. and Penczek, S., to be published.
Stevels, W. M., Ankone, M. J. K., Dijkstra, P. J. and Feijen, J., Macromol. Chem. Phys., 1995, 196, 1153.
Duda, A., Macromolecules, 1994, 27, 576.
In't Veld, P. J. A., Velner, E. M., van de Witte, P., Hamhuis, J., Dijkstra, P. J. and Feijen, J., J. Polym. Sci. Part A: Polym. Chem., 1997, 35, 219.
Song, C. X. and Feng, X. D., Macromolecules, 1984, 17, 2764.
Bero, M., Kasperczyk, J. and Adamus, G., Makromol. Chem., 1993, 194, 907.
Szwarc, M., in Ionic Polymerization Fundamentals. Hanser Publishers, New York, 1996, p. 181.
