Kinetics and Time−Temperature Equivalence of Polymer Degradation
Abstract
We studied the hydrolysis kinetics of amorphous polylactide. It was found the hydrolysis rate had a slow-to-fast transition at a certain molecular weight (Mn). This transition was not correlated with the mass loss and water uptake of samples, nor the pH values of testing media. We speculated that this transition was due to the slow diffusion of polymer chain ends. The chain ends did not significantly promote the hydrolysis of samples until their concentrations (approximately 1/Mn) reached a critical value. The degradation tests were also conducted over a temperature range from 37 to 90 degrees C. A time-temperature equivalent relationship of degradation processes was established and a master curve spanning a time range equivalent to 3-5 years at 37 degrees C was constructed. This master curve can be used to predict polymer degradation processes based on accelerated tests. The functional time and disappearance time of degradable polymers were also discussed.
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The rate of water diffusion depends on the hydrophobicity of the polymer and its shape or surface area while the intrinsic degradation kinetics is affected by the pH and temperature of the medium as well as the molecular weight and microstructures of the polymer.
“The rate of water diffusion depends on the hydrophobicity of the polymer and its shape or surface area while the intrinsic degradation kinetics is affected by the pH 421 and temperature of the medium 422 as well as the molecular weight 423 and microstructures of the polymer.424”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [422]
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- Authors
- Lyu, Schley, J., Loy, B., Lind, D., Hobot, C., Sparer, R., & Untereker, D.
- Affiliations
- Medtronic (United States) (US)
- Corresponding author
- Lyu
- Venue
- Biomacromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-06-19
- Volume
- 8
- Issue
- 7
- Pages
- 2301-2310
- ISSN
- 1525-7797 (ISSN-L)
- 1526-4602
- OpenAlex
- W2008881670
- Cited by
- 237
- References
- 38
- Citations by year
- 2026: 14 · 2025: 25 · 2024: 16 · 2023: 24 · 2022: 14 · 2021: 17 · 2020: 19 · 2019: 14 · 2018: 8 · 2017: 18 · 2016: 11 · 2015: 11 · 2014: 10 · 2013: 7 · 2012: 9
- FWCI
- 2.20
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Biomacromolecules (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Medicine › Hydrogels: synthesis, properties, applications
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Science and PVC
- Keywords
- polylactic acid, hydrolysis kinetics, time-temperature superposition, master curve, accelerated degradation testing, molecular weight dependence, amorphous polymers, degradable polymers, functional time
- MeSH terms
- Hydrogen-Ion Concentration, Hydrolysis, Kinetics, Polymers, Temperature
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