Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers

Watts, Annabelle; Kurokawa, Naruki; Hillmyer, Marc A.

doi:10.1021/acs.biomac.7b00283

Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers

Journal Article · Wed May 03 00:00:00 EDT 2017 · Biomacromolecules

DOI:https://doi.org/10.1021/acs.biomac.7b00283· OSTI ID:1373778

^[1]; Kurokawa, Naruki ^[2]; ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Minnesota, Minneapolis, MN (United States); Keio Univ., Yokohama (Japan)

Thermoplastic elastomers (TPEs) composed of ABA block polymers exhibit a wide variety of properties and are easily processable as they contain physical, rather than chemical, cross-links. Poly(γ-methyl-ε-caprolactone) (PγMCL) is an amorphous polymer with a low entanglement molar mass (M_e = 2.9 kg mol^–1), making it a suitable choice for tough elastomers. Incorporating PγMCL as the midblock with polylactide (PLA) end blocks (f_LA = 0.17) results in TPEs with high stresses and elongations at break (σ_B = 24 ± 2 MPa and ε_B = 1029 ± 20%, respectively) and low levels of hysteresis. The use of isotactic PLA as the end blocks (f_LLA = 0.17) increases the strength and toughness of the material (σ_B = 30 ± 4 MPa, ε_B = 988 ± 30%) due to its semicrystalline nature. This study aims to demonstrate how the outstanding properties in these sustainable materials are a result of the entanglements, glass transition temperature, segment–segment interaction parameter, and crystallinity, resulting in comparable properties to the commercially relevant styrene-based TPEs.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1373778

Journal Information:: Biomacromolecules, Journal Name: Biomacromolecules Journal Issue: 6 Vol. 18; ISSN 1525-7797

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (57)

Melt block copolymerization of ?-caprolactone andL-lactide In't Veld, Peter J. A.; Velner, Esther M.; Van De Witte, Peter Journal of Polymer Science Part A: Polymer Chemistry, Vol. 35, Issue 2 https://doi.org/10.1002/(SICI)1099-0518(19970130)35:2<219::AID-POLA3>3.0.CO;2-N	journal	January 1997
Preparation and stress–strain properties of SBS and SIS block polymers made with dilithium initiators Cunningham, Robert E.; Auerbach, Melvin; Floyd, Walter J. Journal of Applied Polymer Science, Vol. 16, Issue 1 https://doi.org/10.1002/app.1972.070160115	journal	January 1972
Synthesis and characterization of temperature-sensitive block copolymers from poly(N-isopropylacrylamide) and 4-methyl-ε-caprolactone or 4-phenyl-ε-caprolactone Lee, Ren-Shen; Huang, Yi-Ting; Chen, Wen-Hsin Journal of Applied Polymer Science https://doi.org/10.1002/app.32546	journal	January 2010
Selective Nickel-Catalyzed Conversion of Model and Lignin-Derived Phenolic Compounds to Cyclohexanone-Based Polymer Building Blocks Schutyser, Wouter; Van den Bosch, Sander; Dijkmans, Jan ChemSusChem, Vol. 8, Issue 10 https://doi.org/10.1002/cssc.201403375	journal	April 2015
Characterization and degradation of elastomeric four‐armed star copolymers based on caprolactone and L ‐lactide Kong, Jen Fong; Lipik, Vitali; Abadie, Marc J. M. Journal of Biomedical Materials Research Part A, Vol. 100A, Issue 12 https://doi.org/10.1002/jbm.a.34277	journal	July 2012
Triblock Copolymers Based on 1,3-Trimethylene Carbonate and Lactide as Biodegradable Thermoplastic Elastomers Zhang, Zheng; Grijpma, Dirk W.; Feijen, Jan Macromolecular Chemistry and Physics, Vol. 205, Issue 7 https://doi.org/10.1002/macp.200300184	journal	May 2004
Applying the Principles of Green Chemistry to Polymer Production Technology: Applying the Principles of Green Chemistry to Polymer … Dubé, Marc A.; Salehpour, Somaieh Macromolecular Reaction Engineering, Vol. 8, Issue 1 https://doi.org/10.1002/mren.201300103	journal	August 2013
Biodegradable elastomers based on ABA triblocks: influence of end-block crystallinity on elastomeric character: Biodegradable elastomers based on ABA triblocks Kong, Jen Fong; Lipik, Vitali; Abadie, Marc JM Polymer International, Vol. 61, Issue 1 https://doi.org/10.1002/pi.3130	journal	July 2011
Lactone polymers. VI. Glass-transition temperatures of methyl-substituted ε-caprolactones and polymer blends Seefried, C. G.; Koleske, J. V. Journal of Polymer Science: Polymer Physics Edition, Vol. 13, Issue 4 https://doi.org/10.1002/pol.1975.180130416	journal	April 1975
Amphiphilic block copolymers of high-molecular-weight poly(ethylene oxide) and either ε-caprolactone or γ-methyl-ε-caprolactone: Synthesis and characterization: Amphiphilic Block Copolymers Vangeyte, P.; Jérôme, R. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 5 https://doi.org/10.1002/pola.11072	journal	January 2004
Ring-opening polymerization of substituted ɛ-caprolactones with a chiral (salen) AlOiPr complex Breteler, Mark R. Ten; Zhong, Zhiyuan; Dijkstra, Pieter J. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 3 https://doi.org/10.1002/pola.21841	journal	January 2006
Synthesis of biodegradable thermoplastic elastomers from ε -caprolactone and lactide Nakayama, Yuushou; Aihara, Kazuki; Yamanishi, Hitomi Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 3 https://doi.org/10.1002/pola.27463	journal	November 2014
Thermoplastic elastomers Holden, G.; Bishop, E. T.; Legge, N. R. Journal of Polymer Science Part C: Polymer Symposia, Vol. 26, Issue 1 https://doi.org/10.1002/polc.5070260104	journal	January 1969
Hysteresis in rubber vulcanizates: HYSTERESIS IN RUBBER VULCANIZATES Payne, A. R. Journal of Polymer Science: Polymer Symposia, Vol. 48, Issue 1 https://doi.org/10.1002/polc.5070480114	journal	January 1974
Aliphatic polyesters II. The degradation of poly (DL-lactide), poly (ε-caprolactone), and their copolymers in vivo Pitt, G.; Gratzl, M.; Kimmel, G. Biomaterials, Vol. 2, Issue 4 https://doi.org/10.1016/0142-9612(81)90060-0	journal	October 1981
Catalytic aspects in the transformation of pinenes to p-cymene Roberge, Dominique M.; Buhl, Dieter; Niederer, John P. M. Applied Catalysis A: General, Vol. 215, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00514-2	journal	July 2001
Designing biodegradable multiblock PCL/PLA thermoplastic elastomers Cohn, D.; Hotovely Salomon, A. Biomaterials, Vol. 26, Issue 15 https://doi.org/10.1016/j.biomaterials.2004.07.052	journal	May 2005
Pendant small functional groups on poly(ϵ-caprolactone) substrate modulate adhesion, proliferation and differentiation of human mesenchymal stem cells Chen, Min; Zhang, Yi; Zhou, Yan Colloids and Surfaces B: Biointerfaces, Vol. 134 https://doi.org/10.1016/j.colsurfb.2015.07.018	journal	October 2015
Synthesis and characterization of amphiphilic block copolymers from poly(ethylene glycol)methyl ether and 4-methyl-ɛ-caprolactone or 4-phenyl-ɛ-caprolactone Lee, Ren-Shen; Hung, Chia-Bin Polymer, Vol. 48, Issue 9 https://doi.org/10.1016/j.polymer.2007.03.018	journal	April 2007
Processing temperature dependent mechanical response of a thermoplastic elastomer with low hard segment Zhao, Yongsheng; Ning, Nanying; Hu, Xin Polymer, Vol. 53, Issue 19 https://doi.org/10.1016/j.polymer.2012.07.016	journal	August 2012
Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine Biomacromolecules, Vol. 17, Issue 3 https://doi.org/10.1021/acs.biomac.5b01698	journal	February 2016
Renewable, Degradable, and Chemically Recyclable Cross-Linked Elastomers Brutman, Jacob P.; De Hoe, Guilhem X.; Schneiderman, Deborah K. Industrial & Engineering Chemistry Research, Vol. 55, Issue 42 https://doi.org/10.1021/acs.iecr.6b02931	journal	October 2016
Crystallization and Mechanical Properties of Poly( l -lactide)-Based Rubbery/Semicrystalline Multiblock Copolymers Panthani, Tessie R.; Bates, Frank S. Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b01029	journal	June 2015
Aliphatic Polyester Block Polymer Design Schneiderman, Deborah K.; Hillmyer, Marc A. Macromolecules, Vol. 49, Issue 7 https://doi.org/10.1021/acs.macromol.6b00211	journal	March 2016
Mechanical Properties of Star Block Polymer Thermoplastic Elastomers with Glassy and Crystalline End Blocks Burns, Adam B.; Register, Richard A. Macromolecules, Vol. 49, Issue 24 https://doi.org/10.1021/acs.macromol.6b02175	journal	December 2016
Strain-Induced Deformation of Glassy Spherical Microdomains in Elastomeric Triblock Copolymer Films: Simultaneous Measurements of a Stress–Strain Curve with 2d-SAXS Patterns Tomita, Shogo; Lei, Li; Urushihara, Yoshimasa Macromolecules, Vol. 50, Issue 2 https://doi.org/10.1021/acs.macromol.6b02206	journal	January 2017
ABA-Type Thermoplastic Elastomers Composed of Poly(ε-caprolactone- co -δ-valerolactone) Soft Midblock and Polymorphic Poly(lactic acid) Hard End blocks Huang, Yongfeng; Chang, Ruoxing; Han, Lili ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 1 https://doi.org/10.1021/acssuschemeng.5b00855	journal	December 2015
Aliphatic Polyester Block Polymers: Renewable, Degradable, and Sustainable Hillmyer, Marc A.; Tolman, William B. Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar500121d	journal	May 2014
Resorbable and Highly Elastic Block Copolymers from 1,5-Dioxepan-2-one and l -Lactide with Controlled Tensile Properties and Hydrophilicity Ryner, Maria; Albertsson, Ann-Christine Biomacromolecules, Vol. 3, Issue 3 https://doi.org/10.1021/bm015658z	journal	May 2002
Characterization of Polylactide- b -polyisoprene- b -polylactide Thermoplastic Elastomers Frick, Esther M.; Zalusky, Andrew S.; Hillmyer, Marc A. Biomacromolecules, Vol. 4, Issue 2 https://doi.org/10.1021/bm025628b	journal	March 2003
Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications Albertsson, Ann-Christine; Varma, Indra K. Biomacromolecules, Vol. 4, Issue 6 https://doi.org/10.1021/bm034247a	journal	November 2003
ε-Decalactone: A Thermoresilient and Toughening Comonomer to Poly( l -lactide) Olsén, Peter; Borke, Tina; Odelius, Karin Biomacromolecules, Vol. 14, Issue 8 https://doi.org/10.1021/bm400733e	journal	July 2013
Renewable-Resource Thermoplastic Elastomers Based on Polylactide and Polymenthide Wanamaker, Carolyn L.; O'Leary, Leslie E.; Lynd, Nathaniel A. Biomacromolecules, Vol. 8, Issue 11 https://doi.org/10.1021/bm700699g	journal	November 2007
Consequences of Polylactide Stereochemistry on the Properties of Polylactide-Polymenthide-Polylactide Thermoplastic Elastomers Wanamaker, Carolyn L.; Bluemle, Michael J.; Pitet, Louis M. Biomacromolecules, Vol. 10, Issue 10 https://doi.org/10.1021/bm900721p	journal	October 2009
Impact of Morphological Orientation in Determining Mechanical Properties in Triblock Copolymer Systems Honeker, Christian C.; Thomas, Edwin L. Chemistry of Materials, Vol. 8, Issue 8 https://doi.org/10.1021/cm960146q	journal	January 1996
Synthesis and Characterization of Biodegradable Homopolymers and Block Copolymers Based on 1,5-Dioxepan-2-one Loefgren, A.; Albertsson, A. -C.; Dubois, Ph. Macromolecules, Vol. 27, Issue 20 https://doi.org/10.1021/ma00098a007	journal	September 1994
Effect of Volume Fraction on the Order-Disorder Transition in Low Molecular Weight Polystyrene-block-Polyisoprene Copolymers. 1. Order-Disorder Transition Temperature Determined by Rheological Measurements Han, Chang Dae; Baek, Deog Man; Kim, Jin Kon Macromolecules, Vol. 28, Issue 14 https://doi.org/10.1021/ma00118a038	journal	July 1995
Stress Relaxation in Transient Networks of Symmetric Triblock Styrene−Isoprene−Styrene Copolymer Hotta, A.; Clarke, S. M.; Terentjev, E. M. Macromolecules, Vol. 35, Issue 1 https://doi.org/10.1021/ma001976z	journal	January 2002
Consequences of Block Number on the Order−Disorder Transition and Viscoelastic Properties of Linear (AB) _n Multiblock Copolymers Wu, Lifeng; Cochran, Eric W.; Lodge, Timothy P. Macromolecules, Vol. 37, Issue 9 https://doi.org/10.1021/ma035583m	journal	May 2004
Lipase-Catalyzed Ring-Opening Polymerizations of 4-Substituted ε-Caprolactones: Mechanistic Considerations Peeters, Joris W.; van Leeuwen, Oscar; Palmans, Anja R. A. Macromolecules, Vol. 38, Issue 13 https://doi.org/10.1021/ma050510j	journal	June 2005
Aqueous Dispersions of Poly(ethylene oxide)- b -poly(γ-methyl-ε-caprolactone) Block Copolymers Zupancich, John A.; Bates, Frank S.; Hillmyer, Marc A. Macromolecules, Vol. 39, Issue 13 https://doi.org/10.1021/ma060642s	journal	June 2006
Pressure-Sensitive Adhesives from Renewable Triblock Copolymers Shin, Jihoon; Martello, Mark T.; Shrestha, Mona Macromolecules, Vol. 44, Issue 1 https://doi.org/10.1021/ma102216d	journal	January 2011
Polylactide–Poly(6-methyl-ε-caprolactone)–Polylactide Thermoplastic Elastomers Martello, Mark T.; Hillmyer, Marc A. Macromolecules, Vol. 44, Issue 21 https://doi.org/10.1021/ma201063t	journal	November 2011
Uniaxial Extensional Behavior of (SIS) _p -Type Multiblock Copolymer Systems: Structural Origin of High Extensibility Matsumiya, Yumi; Watanabe, Hiroshi; Takano, Atsushi Macromolecules, Vol. 46, Issue 7 https://doi.org/10.1021/ma3026404	journal	March 2013
Reversible Kinetics and Thermodynamics of the Homopolymerization of l -Lactide with 2-Ethylhexanoic Acid Tin(II) Salt Witzke, David R.; Narayan, Ramani; Kolstad, Jeffrey J. Macromolecules, Vol. 30, Issue 23 https://doi.org/10.1021/ma970631m	journal	November 1997
Dependence of the Ultimate Tensile Strength of Thermoplastic Elastomers of the Triblock Type on the Molecular Weight between Chain Entanglements of the Central Block Tong, Jiang-Dong; Jerôme, Robert Macromolecules, Vol. 33, Issue 5 https://doi.org/10.1021/ma990404f	journal	March 2000
Polylactones 48. SnOct ₂ -Initiated Polymerizations of Lactide: A Mechanistic Study Kricheldorf, Hans R.; Kreiser-Saunders, Ingrid; Stricker, Andrea Macromolecules, Vol. 33, Issue 3 https://doi.org/10.1021/ma991181w	journal	February 2000
Bulk Ring-Opening Transesterification Polymerization of the Renewable δ-Decalactone Using an Organocatalyst Martello, Mark T.; Burns, Adam; Hillmyer, Marc ACS Macro Letters, Vol. 1, Issue 1 https://doi.org/10.1021/mz200006s	journal	November 2011
Production of p -Cymene from Crude Sulphate Turpentine with Commercial Zeolite Catalyst Using a Continuous Fixed Bed Reactor Linnekoski, Juha A.; Asikainen, Martta; Heikkinen, Harri Organic Process Research & Development, Vol. 18, Issue 11 https://doi.org/10.1021/op500160f	journal	May 2014
Synthesis and Melt Processing of Sustainable Poly(ε-decalactone)- block -Poly(lactide) Multiblock Thermoplastic Elastomers Martello, Mark T.; Schneiderman, Deborah K.; Hillmyer, Marc A. ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 11 https://doi.org/10.1021/sc500412a	journal	October 2014
Green Chemistry: Principles and Practice Anastas, Paul; Eghbali, Nicolas Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B918763B	journal	January 2010
Recent developments in micellar drug carriers featuring substituted poly(ε-caprolactone)s Rainbolt, Elizabeth A.; Washington, Katherine E.; Biewer, Michael C. Polymer Chemistry, Vol. 6, Issue 13 https://doi.org/10.1039/C4PY01628A	journal	January 2015
Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) copolymer elastomers Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T. Polymer Chemistry, Vol. 6, Issue 19 https://doi.org/10.1039/C5PY00202H	journal	January 2015
Synthesis of biodegradable chiral polyesters by asymmetric enzymatic polymerization and their formulation into microspheres Xiao, Yan; Cummins, David; Palmans, Anja R. A. Soft Matter, Vol. 4, Issue 3 https://doi.org/10.1039/b717059a	journal	January 2008
Theory of Filler Reinforcement Guth, Eugene Journal of Applied Physics, Vol. 16, Issue 1 https://doi.org/10.1063/1.1707495	journal	January 1945
Scalable production of mechanically tunable block polymers from sugar Xiong, M.; Schneiderman, D. K.; Bates, F. S. Proceedings of the National Academy of Sciences, Vol. 111, Issue 23 https://doi.org/10.1073/pnas.1404596111	journal	May 2014
Sustainable Block Copolymer-based Thermoplastic Elastomers [지속 가능한 블록 공중합체 기반 열가소성 탄성체] Shin, Jihoon; Kim, Young-Wun; Kim, Geon-Joong Applied Chemistry for Engineering, Vol. 25, Issue 2 https://doi.org/10.14478/ace.2014-1025	journal	April 2014

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