Unraveling Reactivity Differences: Room-Temperature Ring-Opening Metathesis Polymerization (ROMP) versus Frontal ROMP

Lessard, Jacob J.; Mejia, Edgar B.; Kim, Abbie J.; Zhang, Zhang; Berkey, Mya G.; Medina-Barreto, Zina S.; Ewoldt, Randy H.; Sottos, Nancy R.; Moore, Jeffrey S.

doi:10.1021/jacs.4c01578

Unraveling Reactivity Differences: Room-Temperature Ring-Opening Metathesis Polymerization (ROMP) versus Frontal ROMP

Journal Article · Mon Mar 04 23:00:00 EST 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c01578· OSTI ID:2341316

^[1]; Mejia, Edgar B. ^[2]; Kim, Abbie J. ^[2]; Zhang, Zhang ^[2]; Berkey, Mya G. ^[2]; Medina-Barreto, Zina S. ^[2]; ^[2]; ^[2]; ^[2]

Univ. of Illinois at Urbana-Champaign, IL (United States); REMAT EFRC, University of Illinois Urbana-Champaign
Univ. of Illinois at Urbana-Champaign, IL (United States)

Here, in this study, we explore the distinct reactivity patterns between frontal ring-opening metathesis polymerization (FROMP) and room-temperature solventless ring-opening metathesis polymerization (ROMP). Despite their shared mechanism, we find that FROMP is less sensitive to inhibitor concentration than room-temperature ROMP. By increasing the initiator-to-monomer ratio for a fixed inhibitor/initiator quantity, we find reduction in the ROMP background reactivity at room temperature (i.e., increased resin pot life). At elevated temperatures where inhibitor dissociation prevails, accelerated frontal polymerization rates are observed because of the concentrated presence of the initiator. Surprisingly, the strategy of employing higher initiator loading enhances both pot life and front speeds, which leads to FROMP rates exceeding prior reported values by over 5 times. This counterintuitive behavior is attributed to an increase in the proximity of the inhibitor to the initiator within the bulk resin and to whether the temperature favors coordination or dissociation of the inhibitor. A rapid method was developed for assessing resin pot life, and a straightforward model for active initiator behavior was established. Modified resin systems enabled direct ink writing of robust thermoset structures at rates much faster than previously possible.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023457

OSTI ID:: 2341316

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Self‐Regulative Direct Ink Writing of Frontally Polymerizing Thermoset Polymers Aw, Jia En; Zhang, Xiang; Nelson, Arif Z. Advanced Materials Technologies, Vol. 7, Issue 9 https://doi.org/10.1002/admt.202200230	journal	April 2022
The Ring Opening Metathesis Polymerisation Toolbox Slugovc, Christian Macromolecular Rapid Communications, Vol. 25, Issue 14 https://doi.org/10.1002/marc.200400150	journal	July 2004
Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene Ruiu, Andrea; Sanna, Davide; Alzari, Valeria Journal of Polymer Science Part A: Polymer Chemistry, Vol. 52, Issue 19 https://doi.org/10.1002/pola.27301	journal	July 2014
Durable and impact-resistant thermoset polymers for the extreme environment of low Earth orbit Chang, K. M.; Das, D.; Salvati III., L. Extreme Mechanics Letters, Vol. 64 https://doi.org/10.1016/j.eml.2023.102089	journal	November 2023
Assessing structure/property relationships and synthetic protocols in the fabrication of poly(oxanorbornene imide) single-chain nanoparticles Chen, Ruiwen; Benware, Sarah J.; Cawthern, Sawyer D. European Polymer Journal, Vol. 112 https://doi.org/10.1016/j.eurpolymj.2018.12.046	journal	March 2019
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
Living ring-opening metathesis polymerization Bielawski, Christopher W.; Grubbs, Robert H. Progress in Polymer Science, Vol. 32, Issue 1, p. 1-29 https://doi.org/10.1016/j.progpolymsci.2006.08.006	journal	January 2007
Advances in frontal polymerization strategy: From fundamentals to applications Li, Qing; Shen, Hai-Xia; Liu, Chang Progress in Polymer Science, Vol. 127 https://doi.org/10.1016/j.progpolymsci.2022.101514	journal	April 2022
Poly(peptide): Synthesis, Structure, and Function of Peptide–Polymer Amphiphiles and Protein-like Polymers Callmann, Cassandra E.; Thompson, Matthew P.; Gianneschi, Nathan C. Accounts of Chemical Research, Vol. 53, Issue 2 https://doi.org/10.1021/acs.accounts.9b00518	journal	January 2020
Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction Davydovich, Oleg; Paul, Justine E.; Feist, John David Chemistry of Materials, Vol. 34, Issue 19 https://doi.org/10.1021/acs.chemmater.2c02045	journal	September 2022
Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications Suslick, Benjamin A.; Hemmer, Julie; Groce, Brecklyn R. Chemical Reviews, Vol. 123, Issue 6 https://doi.org/10.1021/acs.chemrev.2c00686	journal	February 2023
Frontal Polymerization of Dicyclopentadiene: A Numerical Study Goli, Elyas; Robertson, Ian D.; Geubelle, Philippe H. The Journal of Physical Chemistry B, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcb.7b12316	journal	April 2018
Survey of Catalysts for Frontal Ring-Opening Metathesis Polymerization Suslick, Benjamin A.; Stawiasz, Katherine J.; Paul, Justine E. Macromolecules, Vol. 54, Issue 11 https://doi.org/10.1021/acs.macromol.1c00566	journal	May 2021
Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis Suslick, Benjamin A.; Alzate-Sanchez, Diego M.; Moore, Jeffrey S. Macromolecules, Vol. 55, Issue 18 https://doi.org/10.1021/acs.macromol.2c01654	journal	September 2022
Rapid Controlled Synthesis of Large Polymers by Frontal Ring-Opening Metathesis Polymerization Alzate-Sanchez, Diego M.; Yu, Christina H.; Lessard, Jacob J. Macromolecules https://doi.org/10.1021/acs.macromol.2c01892	journal	February 2023
Frontal Polymerization of Stereoisomers: Distinct Microstructures and Properties in Endo- and Exo-Dicyclopentadiene Thermosets Wang, Hanlin M.; Suslick, Benjamin A.; Lessard, Jacob J. Macromolecules, Vol. 57, Issue 1 https://doi.org/10.1021/acs.macromol.3c02177	journal	December 2023
Variable Temperature ROMP: Leveraging Low Ring Strain Thermodynamics To Achieve Well-Defined Polypentenamers Neary, William J.; Kennemur, Justin G. Macromolecules, Vol. 50, Issue 13 https://doi.org/10.1021/acs.macromol.7b01148	journal	June 2017
50th Anniversary Perspective : Living Polymerization—Emphasizing the Molecule in Macromolecules Grubbs, Robert B.; Grubbs, Robert H. Macromolecules, Vol. 50, Issue 18 https://doi.org/10.1021/acs.macromol.7b01440	journal	September 2017
Efficient Synthesis of Asymmetric Miktoarm Star Polymers Levi, Adam E.; Fu, Liangbing; Lequieu, Joshua Macromolecules, Vol. 53, Issue 2 https://doi.org/10.1021/acs.macromol.9b02380	journal	January 2020
Efficient Manufacture, Deconstruction, and Upcycling of High-Performance Thermosets and Composites Lloyd, Evan M.; Cooper, Julian C.; Shieh, Peyton ACS Applied Engineering Materials, Vol. 1, Issue 1 https://doi.org/10.1021/acsaenm.2c00115	journal	November 2022
Spontaneous Patterning during Frontal Polymerization Lloyd, Evan M.; Feinberg, Elizabeth C.; Gao, Yuan ACS Central Science, Vol. 7, Issue 4 https://doi.org/10.1021/acscentsci.1c00110	journal	March 2021
Rapid Synthesis of Elastomers and Thermosets with Tunable Thermomechanical Properties Dean, Leon M.; Wu, Qiong; Alshangiti, Omar ACS Macro Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsmacrolett.0c00233	journal	May 2020
Photoexcitation of Grubbs’ Second-Generation Catalyst Initiates Frontal Ring-Opening Metathesis Polymerization Stawiasz, Katherine J.; Paul, Justine E.; Schwarz, Kevin J. ACS Macro Letters, Vol. 9, Issue 11 https://doi.org/10.1021/acsmacrolett.0c00486	journal	October 2020
Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization Stawiasz, Katherine J.; Wendell, Chloe I.; Suslick, Benjamin A. ACS Macro Letters, Vol. 11, Issue 6 https://doi.org/10.1021/acsmacrolett.2c00248	journal	May 2022
Switching Frontal Polymerization Mechanisms: FROMP and FRaP Lessard, Jacob J.; Kaur, Parmeet; Paul, Justine E. ACS Macro Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acsmacrolett.2c00393	journal	August 2022
Frontal Ring-Opening Metathesis Polymerization of Exo-Dicyclopentadiene for Low Catalyst Loadings Robertson, Ian D.; Pruitt, Emmy L.; Moore, Jeffrey S. ACS Macro Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsmacrolett.6b00227	journal	April 2016
Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life Robertson, Ian D.; Dean, Leon M.; Rudebusch, Gabriel E. ACS Macro Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsmacrolett.7b00270	journal	May 2017
Synthesis and Activity of Ruthenium Alkylidene Complexes Coordinated with Phosphine and N-Heterocyclic Carbene Ligands Trnka, Tina M.; Morgan, John P.; Sanford, Melanie S. Journal of the American Chemical Society, Vol. 125, Issue 9 https://doi.org/10.1021/ja021146w	journal	March 2003
Decomposition of a Key Intermediate in Ruthenium-Catalyzed Olefin Metathesis Reactions Hong, Soon Hyeok; Day, Michael W.; Grubbs, Robert H. Journal of the American Chemical Society, Vol. 126, Issue 24 https://doi.org/10.1021/ja0488380	journal	May 2004
Regio- and Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes Kobayashi, Shingo; Pitet, Louis M.; Hillmyer, Marc A. Journal of the American Chemical Society, Vol. 133, Issue 15, p. 5794-5797 https://doi.org/10.1021/ja201644v	journal	March 2011
Cyclic Ruthenium-Alkylidene Catalysts for Ring-Expansion Metathesis Polymerization Boydston, Andrew J.; Xia, Yan; Kornfield, Julia A. Journal of the American Chemical Society, Vol. 130, Issue 38, p. 12775-12782 https://doi.org/10.1021/ja8037849	journal	September 2008
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
Latency for All: Enabling Latency of Hoveyda–Grubbs Second-Generation Catalysts by Adding Phosphite Ligands Vaisman, Anna; Vidavsky, Yuval; Baranov, Mark Journal of the American Chemical Society, Vol. 146, Issue 1 https://doi.org/10.1021/jacs.3c10826	journal	December 2023
A General Approach to Sequence-Controlled Polymers Using Macrocyclic Ring Opening Metathesis Polymerization Gutekunst, Will R.; Hawker, Craig J. Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b04940	journal	June 2015
Bimolecular Coupling as a Vector for Decomposition of Fast-Initiating Olefin Metathesis Catalysts Bailey, Gwendolyn A.; Foscato, Marco; Higman, Carolyn S. Journal of the American Chemical Society, Vol. 140, Issue 22 https://doi.org/10.1021/jacs.8b02709	journal	April 2018
Polymer entanglements Wool, Richard P. Macromolecules, Vol. 26, Issue 7 https://doi.org/10.1021/ma00059a012	journal	March 1993
Frontal Ring-Opening Metathesis Polymerization of Dicyclopentadiene Mariani, Alberto; Fiori, Stefano; Chekanov, Yuri Macromolecules, Vol. 34, Issue 19 https://doi.org/10.1021/ma0106999	journal	September 2001
Understanding Structural Isomerization during Ruthenium-Catalyzed Olefin Metathesis: A Deuterium Labeling Study Courchay, Florence C.; Sworen, John C.; Ghiviriga, Ion Organometallics, Vol. 25, Issue 26 https://doi.org/10.1021/om0509894	journal	November 2006
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
Rapid synchronized fabrication of vascularized thermosets and composites Garg, Mayank; Aw, Jia En; Zhang, Xiang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23054-7	journal	May 2021
Tailored silyl ether monomers enable backbone-degradable polynorbornene-based linear, bottlebrush and star copolymers through ROMP Shieh, Peyton; Nguyen, Hung V. -T.; Johnson, Jeremiah A. Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0352-4	journal	October 2019
Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization Robertson, Ian D.; Yourdkhani, Mostafa; Centellas, Polette J. Nature, Vol. 557, Issue 7704 https://doi.org/10.1038/s41586-018-0054-x	journal	May 2018
Recent advances in ruthenium-based olefin metathesis Ogba, O. M.; Warner, N. C.; O’Leary, D. J. Chemical Society Reviews, Vol. 47, Issue 12 https://doi.org/10.1039/C8CS00027A	journal	January 2018
Protorheology Hossain, Mohammad Tanver; Ewoldt, Randy H. Journal of Rheology, Vol. 68, Issue 1 https://doi.org/10.1122/8.0000667	journal	January 2024
An "Endless" Route to Cyclic Polymers Bielawski, Christopher W.; Benitez, Diego; Grubbs, Robert H. Science, Vol. 297, Issue 5589, p. 2041-2044 https://doi.org/10.1126/science.1075401	journal	September 2002
Decomposition of Ruthenium Olefin Metathesis Catalyst Jawiczuk, Magdalena; Marczyk, Anna; Trzaskowski, Bartosz Catalysts, Vol. 10, Issue 8 https://doi.org/10.3390/catal10080887	journal	August 2020

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