Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

Cater, Henry L.; Allen, Marshall J.; Linnell, Mark I.; Rylski, Adrian K.; Wu, Yudian; Lien, Hsu‐Ming; Mangolini, Filippo; Freeman, Benny D.; Page, Zachariah A.

doi:10.1002/adma.202402431

Title: Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

Journal Article · 07 May 2024 · Advanced Materials

DOI: https://doi.org/10.1002/adma.202402431 · OSTI ID:2370051

^[1];

^[2]; Linnell, Mark I. ^[2];

^[2]; Wu, Yudian ^[2];

^[2];

^[2]

University of Texas at Austin, TX (United States); Center for Materials for Water and Energy Systems (M-WET) at UT Austin
University of Texas at Austin, TX (United States)

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene-based ABA triblock copolymers, this gap is filled. Ring-opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin-like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high-performance plastics (≈260 °C). Here, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next-generation TPEs that are both biologically soft yet thermomechanically durable.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of Texas at Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Robert A. Welch Foundation; Camille & Henry Dreyfus Foundation

Grant/Contract Number:: SC0019272

OSTI ID:: 2370051

Alternate ID(s):: OSTI ID: 2377177

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 30 Vol. 36; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Rapid self-assembly of brush block copolymers to photonic crystals Sveinbjornsson, B. R.; Weitekamp, R. A.; Miyake, G. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 36, p. 14332-14336 https://doi.org/10.1073/pnas.1213055109	journal	August 2012
High χ–Low N Block Polymers: How Far Can We Go? Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00472	journal	September 2015
Sticky Architecture: Encoding Pressure Sensitive Adhesion in Polymer Networks Maw, Mitchell; Dashtimoghadam, Erfan; Keith, Andrew N. ACS Central Science, Vol. 9, Issue 2 https://doi.org/10.1021/acscentsci.2c01407	journal	February 2023
Metal‐Free Ring‐Opening Metathesis Polymerization with Hydrazonium Initiators** Quach, Phong K.; Hsu, Jesse H.; Keresztes, Ivan Angewandte Chemie International Edition, Vol. 61, Issue 24 https://doi.org/10.1002/anie.202203344	journal	April 2022
Evaluation of strain in hydrocarbons. The strain in adamantane and its origin Schleyer, Paul von R.; Williams, James Earl.; Blanchard, K. R. Journal of the American Chemical Society, Vol. 92, Issue 8 https://doi.org/10.1021/ja00711a030	journal	April 1970
Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials Self, Jeffrey L.; Sample, Caitlin S.; Levi, Adam E. Journal of the American Chemical Society, Vol. 142, Issue 16 https://doi.org/10.1021/jacs.0c01467	journal	March 2020
Stretchable Thermoplastic Elastomer Optical Fibers for Sensing of Extreme Deformations Leber, Andreas; Cholst, Beth; Sandt, Joseph Advanced Functional Materials, Vol. 29, Issue 5 https://doi.org/10.1002/adfm.201802629	journal	December 2018
Mechanical biocompatibility of highly deformable biomedical materials Mazza, Edoardo; Ehret, Alexander E. Journal of the Mechanical Behavior of Biomedical Materials, Vol. 48 https://doi.org/10.1016/j.jmbbm.2015.03.023	journal	August 2015
Solvent-free, supersoft and superelastic bottlebrush melts and networks Daniel, William F. M.; Burdyńska, Joanna; Vatankhah-Varnoosfaderani, Mohammad Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4508	journal	November 2015
Phthalate plasticizer di(2‐ethyl‐hexyl) phthalate induces cyclooxygenase‐2 expression in gastric adenocarcinoma cells Wong, Jhen‐Hong; Wang, Yu‐Shiuan; Nam, Sean Environmental Toxicology, Vol. 34, Issue 11 https://doi.org/10.1002/tox.22820	journal	July 2019
Ring-opening metathesis polymerization of 8-membered cyclic olefins Martinez, Henry; Ren, Ning; Matta, Megan E. Polymer Chemistry, Vol. 5, Issue 11 https://doi.org/10.1039/c3py01787g	journal	January 2014
Synthesis of ABA Triblock Copolymers via a Tandem Ring-Opening Metathesis Polymerization: Atom Transfer Radical Polymerization Approach Bielawski, Christopher W.; Morita, Takeharu; Grubbs, Robert H. Macromolecules, Vol. 33, Issue 3 https://doi.org/10.1021/ma990625l	journal	January 2000
Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization Gregory, Georgina L.; Sulley, Gregory S.; Carrodeguas, Leticia Peña Chemical Science, Vol. 11, Issue 25 https://doi.org/10.1039/D0SC00463D	journal	January 2020
Leaching of the plasticizer di(2-ethylhexyl)phthalate (DEHP) from plastic containers and the question of human exposure Erythropel, Hanno C.; Maric, Milan; Nicell, Jim A. Applied Microbiology and Biotechnology, Vol. 98, Issue 24 https://doi.org/10.1007/s00253-014-6183-8	journal	November 2014
Metal-Free Ring-Opening Metathesis Polymerization Ogawa, Kelli A.; Goetz, Adam E.; Boydston, Andrew J. Journal of the American Chemical Society, Vol. 137, Issue 4 https://doi.org/10.1021/ja512073m	journal	January 2015
The ROMP toolbox upgraded Leitgeb, Anita; Wappel, Julia; Slugovc, Christian Polymer, Vol. 51, Issue 14, p. 2927-2946 https://doi.org/10.1016/j.polymer.2010.05.002	journal	June 2010
Mechanically-compliant intracortical implants reduce the neuroinflammatory response Nguyen, Jessica K.; Park, Daniel J.; Skousen, John L. Journal of Neural Engineering, Vol. 11, Issue 5 https://doi.org/10.1088/1741-2560/11/5/056014	journal	August 2014
Approaches to Sustainable and Continually Recyclable Cross-Linked Polymers Fortman, David J.; Brutman, Jacob P.; De Hoe, Guilhem X. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 9 https://doi.org/10.1021/acssuschemeng.8b02355	journal	August 2018
Combining Ring-Opening Metathesis Polymerization and Cyclic Ester Ring-Opening Polymerization To Form ABA Triblock Copolymers from 1,5-Cyclooctadiene and d,l -Lactide Pitet, Louis M.; Hillmyer, Marc A. Macromolecules, Vol. 42, Issue 11 https://doi.org/10.1021/ma900368a	journal	April 2009
Bottlebrush Bridge between Soft Gels and Firm Tissues Keith, Andrew N.; Vatankhah-Varnosfaderani, Mohammad; Clair, Charles ACS Central Science, Vol. 6, Issue 3 https://doi.org/10.1021/acscentsci.9b01216	journal	January 2020
Room temperature 3D printing of super-soft and solvent-free elastomers Xie, Renxuan; Mukherjee, Sanjoy; Levi, Adam E. Science Advances, Vol. 6, Issue 46 https://doi.org/10.1126/sciadv.abc6900	journal	November 2020
Fabrication of New Thermoplastic Polyurethane Elastomers with High Heat Resistance for 3D Printing Derived from 3,3-Dimethyl-4,4′-diphenyl Diisocyanate Hu, Shikai; Shou, Tao; Guo, Mingming Industrial & Engineering Chemistry Research, Vol. 59, Issue 22 https://doi.org/10.1021/acs.iecr.0c01101	journal	May 2020
All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties Lu, Wei; Wang, Yangyang; Wang, Weiyu Polymer Chemistry, Vol. 8, Issue 37 https://doi.org/10.1039/C7PY01225J	journal	January 2017
Plasticizers and Cardiovascular Health: Role of Adipose Tissue Dysfunction Callaghan, Mikyla A.; Alatorre-Hinojosa, Samuel; Connors, Liam T. Frontiers in Pharmacology, Vol. 11 https://doi.org/10.3389/fphar.2020.626448	journal	February 2021
Plasticizer Effects on Physical–Mechanical Properties of Solvent Cast Soluplus® Films Lim, Hanpin; Hoag, Stephen W. AAPS PharmSciTech, Vol. 14, Issue 3 https://doi.org/10.1208/s12249-013-9971-z	journal	May 2013
Amphiphilic ABA triblock copolymers via combination of ROMP and ATRP in ionic liquid: Synthesis, characterization, and self-assembly Xie, Meiran; Kong, Yi; Han, Huijing Reactive and Functional Polymers, Vol. 68, Issue 12 https://doi.org/10.1016/j.reactfunctpolym.2008.09.001	journal	December 2008
Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials Sutthasupa, Sutthira; Shiotsuki, Masashi; Sanda, Fumio Polymer Journal, Vol. 42, Issue 12 https://doi.org/10.1038/pj.2010.94	journal	October 2010
Bridging the gap between rubbers and plastics: a review on thermoplastic polyolefin elastomers Mohite, Aishwarya S.; Rajpurkar, Yash D.; More, Aarti P. Polymer Bulletin, Vol. 79, Issue 2 https://doi.org/10.1007/s00289-020-03522-8	journal	January 2021
Nonlinear elasticity in biological gels Storm, Cornelis; Pastore, Jennifer J.; MacKintosh, F. C. Nature, Vol. 435, Issue 7039 https://doi.org/10.1038/nature03521	journal	May 2005
Thermoplastic Elastomers Holden, Geoffrey Applied Plastics Engineering Handbook https://doi.org/10.1016/B978-1-4377-3514-7.10006-6	book	January 2011
Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan Science, Vol. 359, Issue 6383 https://doi.org/10.1126/science.aar5308	journal	March 2018
Thermoplastic Elastomers with Composite Crystalline−Glassy Hard Domains and Single-Phase Melts Bishop, John P.; Register, Richard A. Macromolecules, Vol. 43, Issue 11 https://doi.org/10.1021/ma100314z	journal	May 2010
Solvothermal Annealing of Block Copolymer Thin Films Gotrik, Kevin W.; Ross, C. A. Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl4021683	journal	October 2013
ROMP of norbornene and oxanorbornene derivatives with pendant fluorophore carbazole and coumarin groups Troiano, Rubina; Carratù, Mario; Pragliola, Stefania European Polymer Journal, Vol. 167 https://doi.org/10.1016/j.eurpolymj.2022.111065	journal	March 2022
Mechanistic and Kinetic Studies of the Ring Opening Metathesis Polymerization of Norbornenyl Monomers by a Grubbs Third Generation Catalyst Hyatt, Michael G.; Walsh, Dylan J.; Lord, Richard L. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b09752	journal	October 2019
Block Copolymer Pressure-Sensitive Adhesives Derived from Fatty Acids and Triacetic Acid Lactone Sajjad, Hussnain; Tolman, William B.; Reineke, Theresa M. ACS Applied Polymer Materials, Vol. 2, Issue 7 https://doi.org/10.1021/acsapm.0c00317	journal	June 2020
Managing Plastic Waste─Sorting, Recycling, Disposal, and Product Redesign Lange, Jean-Paul ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 47 https://doi.org/10.1021/acssuschemeng.1c05013	journal	November 2021
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
The stiffness of living tissues and its implications for tissue engineering Guimarães, Carlos F.; Gasperini, Luca; Marques, Alexandra P. Nature Reviews Materials https://doi.org/10.1038/s41578-019-0169-1	journal	February 2020
ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties Bates, Christopher M.; Chang, Alice B.; Momčilović, Nebojša Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/acs.macromol.5b00880	journal	July 2015
Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers Watts, Annabelle; Kurokawa, Naruki; Hillmyer, Marc A. Biomacromolecules, Vol. 18, Issue 6 https://doi.org/10.1021/acs.biomac.7b00283	journal	May 2017
The Entanglements of Macromolecules and Their Influence on the Properties of Polymers Pawlak, Andrzej Macromolecular Chemistry and Physics, Vol. 220, Issue 10 https://doi.org/10.1002/macp.201900043	journal	April 2019
Waste Rubber Recycling: A Review on the Evolution and Properties of Thermoplastic Elastomers Fazli, Ali; Rodrigue, Denis Materials, Vol. 13, Issue 3 https://doi.org/10.3390/ma13030782	journal	February 2020
Thermoplastic elastomers: fundamentals and applications Spontak, Richard J.; Patel, Nikunj P. Current Opinion in Colloid & Interface Science, Vol. 5, Issue 5-6 https://doi.org/10.1016/S1359-0294(00)00070-4	journal	November 2000
Super-soft, firm, and strong elastomers toward replication of tissue viscoelastic response Dashtimoghadam, Erfan; Maw, Mitchell; Keith, Andrew N. Materials Horizons, Vol. 9, Issue 12 https://doi.org/10.1039/D2MH00844K	journal	January 2022
Synthesis and characterization of hydrogenated poly(norbornene endo-dicarboximide)s prepared by ring opening metathesis polymerization Yoon, Kyung-Hwan; Kim, Kyung Oh; Schaefer, Mark Polymer, Vol. 53, Issue 11 https://doi.org/10.1016/j.polymer.2012.02.047	journal	May 2012
Microcellular Foam from Ethylene Vinyl Acetate/Polybutadiene Rubber (EVA/BR) Based Thermoplastic Elastomers for Footwear Applications Maiti, Madhuchhanda; Jasra, Raksh Vir; Kusum, Suraj K. Industrial & Engineering Chemistry Research, Vol. 51, Issue 32 https://doi.org/10.1021/ie300396m	journal	July 2012
Improved Elastic Recovery from ABC Triblock Terpolymers Albanese, Kaitlin R.; Blankenship, Jacob R.; Quah, Timothy ACS Polymers Au, Vol. 3, Issue 5 https://doi.org/10.1021/acspolymersau.3c00012	journal	July 2023
Foreign Body Reaction to Implanted Biomaterials and Its Impact in Nerve Neuroprosthetics Carnicer-Lombarte, Alejandro; Chen, Shao-Tuan; Malliaras, George G. Frontiers in Bioengineering and Biotechnology, Vol. 9 https://doi.org/10.3389/fbioe.2021.622524	journal	April 2021
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
Impact of Plasticizer on the Intestinal Epithelial Integrity and Tissue-Repairing Ability within Cells in the Proximity of the Human Gut Microbiome Shum, Tim-Fat; Wang, Liwen; Chiou, Jiachi International Journal of Environmental Research and Public Health, Vol. 20, Issue 3 https://doi.org/10.3390/ijerph20032152	journal	January 2023
Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry Wang, Weiyu; Lu, Wei; Goodwin, Andrew Progress in Polymer Science, Vol. 95 https://doi.org/10.1016/j.progpolymsci.2019.04.002	journal	August 2019
Plasticiser loss from plastic or rubber products through diffusion and evaporation Wei, Xin-Feng; Linde, Erik; Hedenqvist, Mikael S. npj Materials Degradation, Vol. 3, Issue 1 https://doi.org/10.1038/s41529-019-0080-7	journal	April 2019
User Guide to Ring-Opening Metathesis Polymerization of endo-Norbornene Monomers with Chelated Initiators Cater, Henry L.; Balynska, Iana; Allen, Marshall J. Macromolecules, Vol. 55, Issue 15 https://doi.org/10.1021/acs.macromol.2c01196	journal	July 2022
A Model Treating Tensile Deformation of Semicrystalline Polymers: Quasi-Static Stress−Strain Relationship and Viscous Stress Determined for a Sample of Polyethylene Hong, K.; Rastogi, A.; Strobl, G. Macromolecules, Vol. 37, Issue 26 https://doi.org/10.1021/ma049174h	journal	December 2004
Catalytic living ring-opening metathesis polymerization with Grubbs’ second- and third-generation catalysts Yasir, Mohammad; Liu, Peng; Tennie, Iris K. Nature Chemistry, Vol. 11, Issue 5 https://doi.org/10.1038/s41557-019-0239-4	journal	April 2019

Similar Records

Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry

Journal Article · 2019 · Progress in Polymer Science · OSTI ID:1546540

Wang, Weiyu; Lu, Wei; Goodwin, Andrew; +5 more

Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers

Journal Article · 2017 · Biomacromolecules · OSTI ID:1373778

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

Dynamic viscoelasticities for short fiber-thermoplastic elastomer composites

Journal Article · 1993 · Journal of Applied Polymer Science; (United States) · OSTI ID:5849689

Guo, Wuyun; Ashida, Michio

Related Subjects

36
Thermoplastic
Elastomers
Norbornene

Title: Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

Citation Formats

References (56)

Similar Records

Related Subjects