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Reversible Kinetics and Thermodynamics of the Homopolymerization of l-Lactide with 2-Ethylhexanoic Acid Tin(II) Salt
Abstract
The reversible kinetics of l -lactide bulk polymerization with tin(II) ethylhexanoate was determined over a wide range of temperatures, 130−220 °C, and monomer to initiator molar ratios, 1000−80 000. Both polymerization and depolymerization are accurately described by a reversible model with a propagation term that is first order in monomer and catalyst. The activation energy of propagation is 70.9 ± 1.5 kJ mol -1 . The enthalpy, entropy, and ceiling temperature of polymerization are −23.3 ± 1.5 kJ mol -1, −22.0 ± 3.2 J mol -1 K -1, and 786 ± 87 °C, respectively. Crystallization increases the propagation rate and decreases the apparent monomer equilibrium in proportion to the degree of crystallinity. Natural hydroxyl impurities stoichiometrically control the polymer molecular weight but do not significantly affect the propagation rate.
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Lewis acid catalyzed polymerization of L-lactide. Kinetics and mechanism of the bulk polymerization
Nijenhuis, A. J., Grijpma, D. W., & Pennings, A. J. (1992) · Macromolecules · doi:10.1021/ma00050a006 · Cited by 407
Crystallization kinetics of poly(l-lactic acid)
Vasanthakumari, R., & Pennings, A. J. (1983) · Polymer · doi:10.1016/0032-3861(83)90129-5 · Cited by 406
McNeill, I. C., & Leiper, H. A. (1985) · Polymer Degradation and Stability · doi:10.1016/0141-3910(85)90035-7 · Cited by 404
Polylactones, 19. Anionic polymerization of L‐lactide in solution
Kricheldorf, H. R., & Kreiser‐Saunders, I. (1990) · Die Makromolekulare Chemie · doi:10.1002/macp.1990.021910508 · Cited by 149
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Poly-lactic acid synthesis for application in biomedical devices — A review
Lasprilla, A. J. R., Martinez, G. A. R., Lunelli, B. H., Jardini, A. L., & Filho, R. M. (2012) · Biotechnology Advances · doi:10.1016/j.biotechadv.2011.06.019 · Cited by 1,174
Carrasco, F., Pagès, P., Gámez-Pérez, J., Santana, O. O., & Maspoch, M. L. (2010) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2009.11.045 · Cited by 738
Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers
Zalusky, A. S., Olayo-Valles, R., Wolf, J. H., & Hillmyer, M. A. (2002) · Journal of the American Chemical Society · doi:10.1021/ja0278584 · Cited by 553
Polylactones 48. SnOct2-Initiated Polymerizations of Lactide: A Mechanistic Study
Kricheldorf, H. R., Kreiser-Saunders, I., & Stricker, A. (2000) · Macromolecules · doi:10.1021/ma991181w · Cited by 467
Poly (Lactic Acid) Production for Tissue Engineering Applications
Lopes, M. S., Jardini, A. L., & Filho, R. M. (2012) · Procedia Engineering · doi:10.1016/j.proeng.2012.07.534 · Cited by 457
Metadata
- Authors
- Witzke, D. R., Narayan, R., & Kolstad, J. J.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 1997-11-01
- Volume
- 30
- Issue
- 23
- Pages
- 7075-7085
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2003443678
- Cited by
- 263
- References
- 6
- FWCI
- 4.79
- Type
- journal article
- Language
- en
- Open access
- closed
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- Witzke, D. R., Narayan, R., & Kolstad, J. J. (1997). Reversible Kinetics and Thermodynamics of the Homopolymerization of l-Lactide with 2-Ethylhexanoic Acid Tin(II) Salt. Macromolecules. https://doi.org/10.1021/ma970631m
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Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
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