Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers
Abstract
Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.
- Authors:
-
- UMM
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- NSFUNIVERSITY
- OSTI Identifier:
- 1183618
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polym. Chem. - UK
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: (19) ; 2015
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Schneiderman, Deborah K., Hill, Erin M., Martello, Mark T., and Hillmyer, Marc A. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers. United States: N. p., 2015.
Web. doi:10.1039/C5PY00202H.
Schneiderman, Deborah K., Hill, Erin M., Martello, Mark T., & Hillmyer, Marc A. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers. United States. https://doi.org/10.1039/C5PY00202H
Schneiderman, Deborah K., Hill, Erin M., Martello, Mark T., and Hillmyer, Marc A. Fri .
"Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers". United States. https://doi.org/10.1039/C5PY00202H. https://www.osti.gov/servlets/purl/1183618.
@article{osti_1183618,
title = {Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers},
author = {Schneiderman, Deborah K. and Hill, Erin M. and Martello, Mark T. and Hillmyer, Marc A.},
abstractNote = {Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.},
doi = {10.1039/C5PY00202H},
journal = {Polym. Chem. - UK},
number = (19) ; 2015,
volume = 6,
place = {United States},
year = {Fri Aug 28 00:00:00 EDT 2015},
month = {Fri Aug 28 00:00:00 EDT 2015}
}
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Works referenced in this record:
Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012
- Matsen, M. W.
- Macromolecules, Vol. 45, Issue 4
Block Copolymers—Designer Soft Materials
journal, February 1999
- Bates, Frank S.; Fredrickson, Glenn H.
- Physics Today, Vol. 52, Issue 2
Block copolymer micelles for drug delivery: design, characterization and biological significance
journal, March 2001
- Kataoka, Kazunori; Harada, Atsushi; Nagasaki, Yukio
- Advanced Drug Delivery Reviews, Vol. 47, Issue 1
Conjugated Block Copolymer Photovoltaics with near 3% Efficiency through Microphase Separation
journal, May 2013
- Guo, Changhe; Lin, Yen-Hao; Witman, Matthew D.
- Nano Letters, Vol. 13, Issue 6
Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013
- Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1
High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation
journal, December 2013
- Schulze, Morgan W.; McIntosh, Lucas D.; Hillmyer, Marc A.
- Nano Letters, Vol. 14, Issue 1
Block Copolymer Thin Films: Physics and Applications
journal, August 2001
- Fasolka, Michael J.; Mayes, Anne M.
- Annual Review of Materials Research, Vol. 31, Issue 1, p. 323-355
Block Copolymer Nanostructures for Technology
journal, October 2010
- Tseng, Yu-Chih; Darling, Seth B.
- Polymers, Vol. 2, Issue 4
Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes
journal, February 2010
- Phillip, William A.; O’Neill, Brandon; Rodwogin, Marc
- ACS Applied Materials & Interfaces, Vol. 2, Issue 3
Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration
journal, June 2010
- Jackson, Elizabeth A.; Hillmyer, Marc A.
- ACS Nano, Vol. 4, Issue 7
Sustainable Poly(lactide- b -butadiene) Multiblock Copolymers with Enhanced Mechanical Properties
journal, September 2013
- Lee, Intaek; Panthani, Tessie R.; Bates, Frank S.
- Macromolecules, Vol. 46, Issue 18
ε-Decalactone: A Thermoresilient and Toughening Comonomer to Poly( l -lactide)
journal, July 2013
- Olsén, Peter; Borke, Tina; Odelius, Karin
- Biomacromolecules, Vol. 14, Issue 8
Triblock Copolymers Based on 1,3-Trimethylene Carbonate and Lactide as Biodegradable Thermoplastic Elastomers
journal, May 2004
- Zhang, Zheng; Grijpma, Dirk W.; Feijen, Jan
- Macromolecular Chemistry and Physics, Vol. 205, Issue 7
Homo- and Block Copolymerizations of ε-Decalactone with l -Lactide Catalyzed by Lanthanum Compounds
journal, September 2013
- Lin, Jin-Ou; Chen, Wanli; Shen, Zhiquan
- Macromolecules, Vol. 46, Issue 19
Polylactide–Poly(6-methyl-ε-caprolactone)–Polylactide Thermoplastic Elastomers
journal, November 2011
- Martello, Mark T.; Hillmyer, Marc A.
- Macromolecules, Vol. 44, Issue 21
Resorbable and Highly Elastic Block Copolymers from 1,5-Dioxepan-2-one and l -Lactide with Controlled Tensile Properties and Hydrophilicity
journal, May 2002
- Ryner, Maria; Albertsson, Ann-Christine
- Biomacromolecules, Vol. 3, Issue 3
Renewable-Resource Thermoplastic Elastomers Based on Polylactide and Polymenthide
journal, November 2007
- Wanamaker, Carolyn L.; O'Leary, Leslie E.; Lynd, Nathaniel A.
- Biomacromolecules, Vol. 8, Issue 11
Scalable production of mechanically tunable block polymers from sugar
journal, May 2014
- Xiong, M.; Schneiderman, D. K.; Bates, F. S.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 23
Synthesis and Melt Processing of Sustainable Poly(ε-decalactone)- block -Poly(lactide) Multiblock Thermoplastic Elastomers
journal, October 2014
- Martello, Mark T.; Schneiderman, Deborah K.; Hillmyer, Marc A.
- ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 11
Controlled Polymerization of Next-Generation Renewable Monomers and Beyond
journal, February 2013
- Yao, Kejian; Tang, Chuanbing
- Macromolecules, Vol. 46, Issue 5
Biobased building blocks for the rational design of renewable block polymers
journal, January 2014
- Holmberg, Angela L.; Reno, Kaleigh H.; Wool, Richard P.
- Soft Matter, Vol. 10, Issue 38
Biodegradable Polyesters from Renewable Resources
journal, June 2013
- Tsui, Amy; Wright, Zachary C.; Frank, Curtis W.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 4, Issue 1
The battle for the “green” polymer. Different approaches for biopolymer synthesis: bioadvantaged vs. bioreplacement
journal, January 2014
- Hernández, Nacú; Williams, R. Christopher; Cochran, Eric W.
- Org. Biomol. Chem., Vol. 12, Issue 18
PLA-based biodegradable and tunable soft elastomers for biomedical applications
journal, November 2011
- Harrane, Amine; Leroy, Adrien; Nouailhas, Hélène
- Biomedical Materials, Vol. 6, Issue 6
Synthesis, preparation, in vitro degradation, and application of novel degradable bioelastomers—A review
journal, May 2012
- Liu, Quanyong; Jiang, Lei; Shi, Rui
- Progress in Polymer Science, Vol. 37, Issue 5
Dependence of the Ultimate Tensile Strength of Thermoplastic Elastomers of the Triblock Type on the Molecular Weight between Chain Entanglements of the Central Block
journal, March 2000
- Tong, Jiang-Dong; Jerôme, Robert
- Macromolecules, Vol. 33, Issue 5
Aliphatic polyesters II. The degradation of poly (DL-lactide), poly (ε-caprolactone), and their copolymers in vivo
journal, October 1981
- Pitt, G.; Gratzl, M.; Kimmel, G.
- Biomaterials, Vol. 2, Issue 4
Triblock copolymers of -caprolactone, trimethylene carbonate, and L-lactide: Effects of using random copolymer as hard-block
journal, February 2012
- Widjaja, Leonardus Kresna; Kong, Jen Fong; Chattopadhyay, Sujay
- Journal of the Mechanical Behavior of Biomedical Materials, Vol. 6
Designing biodegradable multiblock PCL/PLA thermoplastic elastomers
journal, May 2005
- Cohn, D.; Hotovely Salomon, A.
- Biomaterials, Vol. 26, Issue 15
Synthesis and Properties of Poly[isobornyl methacrylate (IBMA)- b -butadiene (BD)- b -IBMA] Copolymers: New Thermoplastic Elastomers of a Large Service Temperature Range
journal, January 1996
- Yu, Jian Ming; Dubois, Philippe; Jérôme, Robert
- Macromolecules, Vol. 29, Issue 23
Triblock copolymers of ε-caprolactone, L-lactide, and trimethylene carbonate: Biodegradability and elastomeric behavior
journal, July 2011
- Widjaja, Leonardus Kresna; Kong, Jen Fong; Chattopadhyay, Sujay
- Journal of Biomedical Materials Research Part A, Vol. 99A, Issue 1
Synthesis of biodegradable thermoplastic elastomers (BTPE) based on ε-caprolactone
journal, January 2010
- Lipik, V. T.; Widjaja, L. K.; Liow, S. S.
- Express Polymer Letters, Vol. 4, Issue 1
Poly(CL/DLLA-b-CL) multiblock copolymers as biodegradable thermoplastic elastomers
journal, January 2008
- Ryynanen, T.; Nykanen, A.; Seppala, J. V.
- Express Polymer Letters, Vol. 2, Issue 3
Resilient Bioresorbable Copolymers Based on Trimethylene Carbonate, l -Lactide, and 1,5-Dioxepan-2-one
journal, May 2006
- Andronova, Natalia; Albertsson, Ann-Christine
- Biomacromolecules, Vol. 7, Issue 5
Biodegradable elastomers based on ABA triblocks: influence of end-block crystallinity on elastomeric character: Biodegradable elastomers based on ABA triblocks
journal, July 2011
- Kong, Jen Fong; Lipik, Vitali; Abadie, Marc JM
- Polymer International, Vol. 61, Issue 1
Thermoplastic elastomers based on poly(lactide)–poly(trimethylene carbonate-co-caprolactone)–poly(lactide) triblock copolymers and their stereocomplexes
journal, November 2006
- Zhang, Z.; Grijpma, D. W.; Feijen, J.
- Journal of Controlled Release, Vol. 116, Issue 2
Enhancement of mechanical properties of triblock copolymers by random copolymer middle blocks
journal, June 2007
- Staudinger, Ulrike; Satapathy, Bhabani K.; Thunga, Mahendra
- European Polymer Journal, Vol. 43, Issue 6
Regular Mixing Thermodynamics of Hydrogenated Styrene–Isoprene Block–Random Copolymers
journal, April 2013
- Beckingham, Bryan S.; Register, Richard A.
- Macromolecules, Vol. 46, Issue 8
Mixing Thermodynamics of Ternary Block–Random Copolymers Containing a Polyethylene Block
journal, March 2013
- Beckingham, Bryan S.; Burns, Adam B.; Register, Richard A.
- Macromolecules, Vol. 46, Issue 7
Synthesis of biodegradable thermoplastic elastomers from ε -caprolactone and lactide
journal, November 2014
- Nakayama, Yuushou; Aihara, Kazuki; Yamanishi, Hitomi
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 3
Topological behavior mimicking ethylene–hexene copolymers using branched lactones and macrolactones
journal, January 2014
- Jasinska-Walc, Lidia; Hansen, Michael Ryan; Dudenko, Dmytro
- Polym. Chem., Vol. 5, Issue 10
Achieving Micelle Control through Core Crystallinity
journal, October 2013
- Glavas, Lidija; Olsén, Peter; Odelius, Karin
- Biomacromolecules, Vol. 14, Issue 11
Effect of composition on the entanglement density in random copolymers
journal, July 1990
- Lomellini, Paolo; Rossi, Anna Grazia
- Die Makromolekulare Chemie, Vol. 191, Issue 7, p. 1729-1737
Kinetics and Mechanism of the Stannous Octoate-Catalyzed Bulk Polymerization of ε-Caprolactone
journal, February 2002
- Storey, Robson F.; Sherman, John W.
- Macromolecules, Vol. 35, Issue 5
Crystallization kinetics of poly(ε-caprolactone) in miscible thermosetting polymer blends of epoxy resin and poly(ε-caprolactone)
journal, October 2001
- Guo, Qipeng; Groeninckx, Gabriel
- Polymer, Vol. 42, Issue 21
Crystal structure of poly-ε-caprolactone
journal, December 1970
- Bittiger, H.; Marchessault, R. H.; Niegisch, W. D.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 26, Issue 12
Synthesis, characterization, and miscibility of caprolactone random copolymers
journal, July 1986
- Vion, Jean Marc; Jerome, Robert; Teyssie, Philippe
- Macromolecules, Vol. 19, Issue 7
Crystallization kinetics and melting of caprolactone random copolymers
journal, November 1990
- Goulet, Louise; Prud'homme, Robert E.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 28, Issue 12
Lactone polymers. VIII. Dynamic mechanical properties of ε-caprolactone and γ-(tert-butyl)-ε-caprolactone copolymers
journal, November 1976
- Seefried, C. G.; Koleske, J. V.; Critchfield, F. E.
- Journal of Polymer Science: Polymer Physics Edition, Vol. 14, Issue 11
Ring-Opening Polymerization of l -Lactide and ε-Caprolactone Utilizing Biocompatible Zinc Catalysts. Random Copolymerization of l -Lactide and ε-Caprolactone
journal, November 2010
- Darensbourg, Donald J.; Karroonnirun, Osit
- Macromolecules, Vol. 43, Issue 21
Crystallization behavior of poly(ε-caprolactone) chains confined in lamellar nanodomains
journal, August 2014
- Nakagawa, Shintaro; Tanaka, Takumi; Ishizone, Takashi
- Polymer, Vol. 55, Issue 16
Rheology of ordered and disordered symmetric poly(ethylenepropylene)-poly(ethylethylene) diblock copolymers
journal, April 1990
- Rosedale, J. H.; Bates, F. S.
- Macromolecules, Vol. 23, Issue 8
Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- b -PCL Diblock Copolymers
journal, May 2010
- Castillo, Reina Verónica; Müller, Alejandro J.; Raquez, Jean-Marie
- Macromolecules, Vol. 43, Issue 9
Crystallization in Poly( l -lactide)- b -poly(ε-caprolactone) Double Crystalline Diblock Copolymers: A Study Using X-ray Scattering, Differential Scanning Calorimetry, and Polarized Optical Microscopy
journal, January 2005
- Hamley, I. W.; Castelletto, V.; Castillo, R. V.
- Macromolecules, Vol. 38, Issue 2
Melt Structure and its Transformation by Sequential Crystallization of the Two Blocks within Poly(L-lactide)-block-Poly(ɛ-caprolactone) Double Crystalline Diblock Copolymers
journal, June 2006
- Hamley, I. W.; Parras, P.; Castelletto, V.
- Macromolecular Chemistry and Physics, Vol. 207, Issue 11
Crystallization-Induced Orientation for Microstructures of Poly( l -lactide)- b -poly(ε-caprolactone) Diblock Copolymers
journal, December 2003
- Ho, Rong-Ming; Hsieh, Ping-Yen; Tseng, Wen-Hsien
- Macromolecules, Vol. 36, Issue 24
Synthesis and crystallization behavior of poly( l -lactide)- block -poly(ϵ-caprolactone) copolymer
journal, August 2001
- Kim, Jin Kon; Park, Dong-Jin; Lee, Myung-Se
- Polymer, Vol. 42, Issue 17
Thermal properties of di- and triblock copolymers of poly(l-lactide) with poly(oxyethylene) or poly(ε-caprolactone)
journal, January 2003
- Maglio, Giovanni; Migliozzi, Anna; Palumbo, Rosario
- Polymer, Vol. 44, Issue 2
Synthesis and Characterization of Poly( l -lactide)−Poly(ε-caprolactone) Multiblock Copolymers
journal, July 2003
- Jeon, Oju; Lee, Soo-Hong; Kim, Soo Hyun
- Macromolecules, Vol. 36, Issue 15
Structure and mechanical properties of poly(?,?-lactic acid)/poly(ɛ-caprolactone) blends
journal, October 2003
- Broz, M.
- Biomaterials, Vol. 24, Issue 23
Nanoporous Linear Polyethylene from a Block Polymer Precursor
journal, June 2010
- Pitet, Louis M.; Amendt, Mark A.; Hillmyer, Marc A.
- Journal of the American Chemical Society, Vol. 132, Issue 24
Pressure-Sensitive Adhesives from Renewable Triblock Copolymers
journal, January 2011
- Shin, Jihoon; Martello, Mark T.; Shrestha, Mona
- Macromolecules, Vol. 44, Issue 1
Consequences of Polylactide Stereochemistry on the Properties of Polylactide-Polymenthide-Polylactide Thermoplastic Elastomers
journal, October 2009
- Wanamaker, Carolyn L.; Bluemle, Michael J.; Pitet, Louis M.
- Biomacromolecules, Vol. 10, Issue 10
A correlation between critical tensile strength and polymer cross-sectional area
journal, December 1972
- Vincent, P. I.
- Polymer, Vol. 13, Issue 12
Bulk polymerization of ε-caprolactone: Rheological predictive laws
journal, May 2000
- Gimenez, Jérôme; Cassagnau, Philippe; Michel, Alain
- Journal of Rheology, Vol. 44, Issue 3
Block copolymer micelles for drug delivery: Design, characterization and biological significance
journal, December 2012
- Kataoka, Kazunori; Harada, Atsushi; Nagasaki, Yukio
- Advanced Drug Delivery Reviews, Vol. 64
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journal, November 2018
- Konwar, Debanga B.; Satapathy, Bhabani K.; Jacob, Josemon
- Polymer International, Vol. 68, Issue 3
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journal, January 2020
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- Polymer International, Vol. 69, Issue 4
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journal, January 2019
- D'Auria, Ilaria; D'Alterio, Massimo Christian; Tedesco, Consiglia
- RSC Advances, Vol. 9, Issue 56