Rheological Behavior and Modeling of Thermal Degradation of Poly(∊-Caprolactone) and Poly(L-Lactide)
-
A. López Arraiza
Abstract
Growing environmental concerns have led to the development of alternative biodegradable polymers with properties comparable to the conventional poly(ethylene), poly(propylene) or poly(ethylene terephthalate). In this paper the thermal degradation of poly(∊-caprolactone) (PCL) and poly(L-lactide) (PLLA) melts was investigated by rheometry and thermogravimetry under different temperatures and inert atmosphere. The chain scission process was modeled to explain the phenomenon. The analysis suggests that PLLA is degraded by an unzipping depolymerization process from the hydroxyl end of the polymer chains. In contrast, the thermal degradation behavior of PCL was very complex because various reactions occurred concurrently: post-polymerization, loss of structural regularities and random chain scissions.
References
Abe, H., et al., “Effects of Residual Zinc Compounds and Chain-end Structure on Thermal Degradation of Poly(∊-caprolactone)”, Biomacromolecules, 5, 1480–1488 (2004)10.1021/bm049945pSearch in Google Scholar
Abe, H., et al., “Thermal Degradation Processes of End-Capped Poly(L-lactide)s in the Presence and Absence of Residual Zinc Catalyst”, Biomacromolecules, 5, 1606–1614 (2004)10.1021/bm0497872Search in Google Scholar
Andriano, K., et al., “Processing and Characterization of Absorbable Polylactide Polymers for Use in Surgical Implants”, J. Appl. Biomater., 5, 133–140 (1994)10.1002/jab.770050206Search in Google Scholar
Aoyagi, Y., et al., “Thermal Degradation of Poly[(R)-3-hydroxybutyrate], Poly[∊-caprolactone], and Poly[(S)-lactide]”, Polym. Degrad. Stab., 76, 53–59 (2002)10.1016/S0141-3910(01)00265-8Search in Google Scholar
Assadi, R., et al., “Irreversible Structural Changes during PET Recycling by Extrusion”, Polymer, 45, 4403–4412 (2004)10.1016/j.polymer.2004.04.029Search in Google Scholar
Brostroem, J., et al., “Biodegradable Films of Partly Branched Poly(L-lactide)-co-poly(∊-caprolactone) Copolymer: Modulation of Phase Morphology, Plasticization Properties and Thermal Depolymerization”, Biomacromolecules, 5, 1124–1134 (2004)10.1021/bm049920qSearch in Google Scholar
Di Maioa, E., et al., “Isothermal Cystallization in PCL/clay Nonocomposites Investigated with Thermal and Rheometric Methods”, Polymer, 45, 8893–8900 (2004)10.1016/j.polymer.2004.10.037Search in Google Scholar
Dwan, I., et al., “Hydrolytic and Thermal Degradation of Random Copolyesters of ∊-caprolactone and 2-oxepane-1,5-dione”, Macromol. Chem. Phys., 204, 1191–1201 (2003)10.1002/macp.200390092Search in Google Scholar
Engerberg, I., Kohn, J., “Physico-mechanical Properties of Degradable Polymers used in Medical Applications: A Comparative Study”, Biomaterials, 12, 292–304 (1991)10.1016/0142-9612(91)90037-BSearch in Google Scholar
Hideto, T., Ippei, F., “Enhanced Thermal Stability of Poly(lactide)s in the Melt by Enantiomeric Polymer Blending”, Polymer, 44, 2891–2896 (2003)10.1016/S0032-3861(03)00175-7Search in Google Scholar
Hofmann, G., Wagner, F., “New Implant Designs for Bioresorbable Devices In Orthopaedic Surgery”, Clin. Mat., 14, 207–215 (1993)10.1016/0267-6605(93)90004-QSearch in Google Scholar
Li, S., et al., “Hydrolytic Degradation of Poly(DL-lactic acid) Further Investigations”, Polymer Preprints, 37, 133–134 (1996)Search in Google Scholar
Persenaire, O., Alexandre, M., Degee, P., Dubois, P., “Mechanisms and Kinetics of Thermal Degradation of Poly(∊-caprolactone)”, Biomacromolecules, 2, 288–294 (2001)10.1021/bm0056310Search in Google Scholar
Placketta, D., et al., “Biodegradable Composites based on L-polylactide and Jute Fibres”, Compos. Sci. Technol., 63, 1287–1296 (2003)10.1016/S0266-3538(03)00100-3Search in Google Scholar
Raquez, J.-M., et al., “Diblock Copolymers based on 1,4-dioxan-2-one and ∊-Caprolactone: Characterization and Thermal Properties”, Macromol. Chem. Phys.”, 205, 1764–1773 (2004)Search in Google Scholar
Ruseckaite, R.-A., Jimenez, A., “Thermal Degradation of Mixtures of Polycaprolactone with Cellulose Derivatives”, Polym. Degrad. Stab., 81, 353–358 (2003)10.1016/S0141-3910(03)00106-XSearch in Google Scholar
Saito, O.: “Chapter 11 The Radiation Chemistry of Macromolecules”, in: Dole, M., (Ed.), Vol. 1, Academic Press, New York (1972)Search in Google Scholar
Sarasua, J.-R., et al., “Crystallinity and Mechanical Properties of Optically Pure Polylactides and Their Blends”, Polym. Eng. Sci., 45, 745–753 (2005)10.1002/pen.20331Search in Google Scholar
Sarasua, J.-R., et al., “Crystallization, Morphology, and Mechanical Behavior of Polylactide/Poly(∊-caprolactone) Blends”, Polym. Eng. Sci., 46, 1299–1308 (2006)10.1002/pen.20609Search in Google Scholar
Schindler, A., Harper, J., “Polylactide. II. Viscosity-molecular Weight Relationships and Unperturbed Chain Dimensions”, J. Polym. Sci. Part A: Polym. Chem., 17, 2593–2599 (1979)10.1002/pol.1979.170170831Search in Google Scholar
Schindler, A., et al., “Aliphatic Polyesters. III. Molecular Weight and Molecular Weight Distribution in Alcohol-Initiated Polymerizations of ∊-caprolactone”, J. Polym. Sci. Part A: Polym. Chem., 20, 319–326 (1982)10.1002/pol.1982.170200206Search in Google Scholar
Shirahase, T., et al., “Miscibility and Hydrolytic Degradation in Alkaline Solution of Poly(L-lactide) and Poly(methyl methacrylate) Blends”, Polymer, 47, 4839–4844 (2006)10.1016/j.polymer.2006.04.012Search in Google Scholar
Sivalingam, G., et al., “Kinetics of Thermal Degradation of Poly(∊-caprolactone)”, J. Anal. Appl. Pyrolysis, 70, 631–647 (2003)10.1016/S0165-2370(03)00045-7Search in Google Scholar
Sivalingam, G., et al., “Blends of Poly(∊-caprolactone) and Poly(vinyl acetate): Mechanical Properties and Thermal Degradation”, Polym. Degrad. Stab., 84, 345–351 (2004)10.1016/j.polymdegradstab.2004.01.011Search in Google Scholar
Sivalingam, G., Madras, G., “Thermal Degradation of Binary Physical Mixtures and Copolymers of Poly(∊-caprolactone), Poly(D, L-lactide), Poly(glycolide)”, Polym. Degrad. Stab., 84, 393–398 (2004)10.1016/j.polymdegradstab.2003.12.008Search in Google Scholar
Sivalingam, G., Madras, G., “Thermal Degradation of Ternary Blends of Poly(e-ocaprolactone)/Poly(vinyl acetate)/Poly(vinyl chloride)”, J. Appl. Polym. Sci., 93, 1378–1383 (2004)10.1002/app.20587Search in Google Scholar
Sivalingam, G., et al., “Enzymatic and Thermal Degradation of Poly(∊-caprolactone), Poly(D, L-lactide), and Their Blends”, Ind. Eng. Chem. Res., 43, 7702–7709 (2004)10.1021/ie049589rSearch in Google Scholar
Soedergard, A., Naesman, J.-H., “Stabilization of Poly(L-lactide) in the Melt”, Polym. Degrad. Stab., 46, 25–30 (1994)10.1016/0141-3910(94)90104-XSearch in Google Scholar
Suprakas, S.-R., et al., “New Polylactide-layered Silicate Nanocomposites. 2. Concurrent Improvements of Material Properties, Biodegradability and Melt Rheology”, Polymer, 44, 857–866 (2003)10.1016/S0032-3861(02)00818-2Search in Google Scholar
Taubner, V., Shishoo, R. “Influence of Processing Parameters on the Degradation of Poly(L-lactide) during Extrusion”, J. Appl. Polym. Sci., 79, 2128–2135 (2001)10.1002/1097-4628(20010321)79:12<2128::AID-APP1020>3.0.CO;2-#Search in Google Scholar
Woo, S., et al., “Biomechanics of Knee Ligament Healing, Repair and Reconstruction”, J. Biomechanics, 30, 431–439 (1997)10.1016/S0021-9290(96)00168-6Search in Google Scholar
© 2007, Carl Hanser Verlag, Munich
Articles in the same Issue
- Contents
- Contents
- Editorial
- Special Issue on Biobased Polymers
- Invited Papers
- Crystallization and Mechanical Propertiesof Poly (D, L) Lactide-based Blown Films
- Rheological Behavior and Modeling of Thermal Degradation of Poly(∊-Caprolactone) and Poly(L-Lactide)
- Rheological Evaluation and Observations of Extrusion Instabilities of Biodegradable Polyesters
- Biaxial Orientation of Polylactide/Thermoplastic Starch Blends
- Effects of Starch Types on Mechanical Properties of Poly(lactic acid)/Starch Composites
- Solid and Microcellular Polylactide-Carbon Nanotube Nanocomposites
- Tapioca Starch-poly (lactic acid)-based Nanocomposite Foams as Affected by Type of Nanoclay
- Injection Molded Solid and Microcellular Polylactide Compounded with Recycled Paper Shopping Bag Fibers
- Fabrication of Porous 3-D Structure from Poly(L-lactide)-based Nanocomposite Foam via Enzymatic Degradation
- The Linear Viscoelastic Behavior of a Series of 3-Hydroxybutyrate-based Copolymers
- New Developments in Biodegradable Starch-based Nanocomposites
- Viscous Properties of Thermoplastic Starches from Different Botanical Origin
- Thermoplastic Foams from Zein and Gelatin
- Improvement of the Mechanical Properties of Soy Protein Isolate Based Plastics through Formulation and Processing
- Biocomposites Based on Bacterial Cellulose and Apple and Radish Pulp
- Preparation and Properties of Metallocene-catalyzed PE/Starch Nanocomposites: Role of Nanocompatibilizer
- Evaluation of Properties and Biodeterioration Potential of Polyethylene and Aliphatic Polyester Blends
- PPS News
- PPP News
- Seikei-Kakou Abstracts
- Seikei-Kakou Abstracts
Articles in the same Issue
- Contents
- Contents
- Editorial
- Special Issue on Biobased Polymers
- Invited Papers
- Crystallization and Mechanical Propertiesof Poly (D, L) Lactide-based Blown Films
- Rheological Behavior and Modeling of Thermal Degradation of Poly(∊-Caprolactone) and Poly(L-Lactide)
- Rheological Evaluation and Observations of Extrusion Instabilities of Biodegradable Polyesters
- Biaxial Orientation of Polylactide/Thermoplastic Starch Blends
- Effects of Starch Types on Mechanical Properties of Poly(lactic acid)/Starch Composites
- Solid and Microcellular Polylactide-Carbon Nanotube Nanocomposites
- Tapioca Starch-poly (lactic acid)-based Nanocomposite Foams as Affected by Type of Nanoclay
- Injection Molded Solid and Microcellular Polylactide Compounded with Recycled Paper Shopping Bag Fibers
- Fabrication of Porous 3-D Structure from Poly(L-lactide)-based Nanocomposite Foam via Enzymatic Degradation
- The Linear Viscoelastic Behavior of a Series of 3-Hydroxybutyrate-based Copolymers
- New Developments in Biodegradable Starch-based Nanocomposites
- Viscous Properties of Thermoplastic Starches from Different Botanical Origin
- Thermoplastic Foams from Zein and Gelatin
- Improvement of the Mechanical Properties of Soy Protein Isolate Based Plastics through Formulation and Processing
- Biocomposites Based on Bacterial Cellulose and Apple and Radish Pulp
- Preparation and Properties of Metallocene-catalyzed PE/Starch Nanocomposites: Role of Nanocompatibilizer
- Evaluation of Properties and Biodeterioration Potential of Polyethylene and Aliphatic Polyester Blends
- PPS News
- PPP News
- Seikei-Kakou Abstracts
- Seikei-Kakou Abstracts