Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Davydovich, Oleg; Paul, Justine E.; Feist, John David; Aw, Jia En; Balta Bonner, Francisco Javier; Lessard, Jacob J.; Tawfick, Sameh; Xia, Yan; Sottos, Nancy R.; Moore, Jeffrey S.

doi:10.1021/acs.chemmater.2c02045

Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Journal Article · Wed Sep 21 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c02045· OSTI ID:2370403

^[1]; Paul, Justine E. ^[2]; ^[3]; Aw, Jia En ^[2]; Balta Bonner, Francisco Javier ^[2]; ^[2]; ^[2]; ^[3]; ^[2]; ^[2]

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

Frontal ring-opening metathesis polymerization (FROMP) is a rapid, low-energy manufacturing reaction that is useful for curing thermosetting materials. FROMP of dicyclopentadiene (DCPD) results in poly(dicyclopentadiene) (p(DCPD)), a tough thermoset with excellent mechanical performance and chemical stability. Like most thermosets, p(DCPD) cannot be reprocessed and is therefore difficult to recycle. Previous work demonstrated that the incorporation of a small quantity of cleavable units in the strand segments of p(DCPD) networks enables their deconstruction. Here, we report that a commercially available multifunctional comonomer, 2,3-dihydrofuran (DHF), both acts as a potent Grubbs catalyst inhibitor during FROMP and introduces acid cleavable units. The resulting materials retain high performance characteristics, including glass-transition temperatures ranging from 115 to 165 °C and ultimate strength ranging from 35 to 40 MPa. The addition of DHF above critical loading levels enables deconstructable thermosets. Here, we further demonstrate freeform three-dimensional (3D) printing of deconstructable thermosets via frontal polymerization.

View Accepted Manuscript (DOE)

Research Organization:: University 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:: 2370403

Alternate ID(s):: OSTI ID: 1981831

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (38)

Frontal curing of epoxy resins: Comparison of mechanical and thermal properties to batch-cured materials Chekanov, Yuri; Arrington, David; Brust, Greg Journal of Applied Polymer Science, Vol. 66, Issue 6 https://doi.org/10.1002/(SICI)1097-4628(19971107)66:6<1209::AID-APP20>3.0.CO;2-V	journal	November 1997
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
Cure-on-demand wood adhesive based on the frontal polymerization of acrylates: Cure-On-Demand Wood Adhesive Holt, TreyVon; Fazende, Kylee; Jee, Elizabeth Journal of Applied Polymer Science, Vol. 133, Issue 40 https://doi.org/10.1002/app.44064	journal	July 2016
Synthesis of new telechelic oligomers and macro-monomers by “constructive degradation” Ebdon, John R. Macromolecular Symposia, Vol. 84, Issue 1 https://doi.org/10.1002/masy.19940840108	journal	July 1994
UV-ignited frontal polymerization of an epoxy resin Mariani, Alberto; Bidali, Simone; Fiori, Stefano Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 9 https://doi.org/10.1002/pola.20051	journal	January 2004
Frontal cationic curing of epoxy resins Scognamillo, Sergio; Bounds, Chris; Luger, Michael Journal of Polymer Science Part A: Polymer Chemistry, Vol. 48, Issue 9 https://doi.org/10.1002/pola.23967	journal	May 2010
Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene Alzari, Valeria; Nuvoli, Daniele; Sanna, Davide Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 1 https://doi.org/10.1002/pola.27776	journal	August 2015
Degradable precision polynorbornenes via ring-opening metathesis polymerization Moatsou, Dafni; Nagarkar, Amit; Kilbinger, Andreas F. M. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 9 https://doi.org/10.1002/pola.27964	journal	November 2015
The effect of acrylate functionality on frontal polymerization velocity and temperature Bynum, Samuel; Tullier, Michael; Morejon‐Garcia, Catherine Journal of Polymer Science Part A: Polymer Chemistry, Vol. 57, Issue 9 https://doi.org/10.1002/pola.29352	journal	March 2019
Recycling technologies for thermoset composite materials—current status Pickering, S. J. Composites Part A: Applied Science and Manufacturing, Vol. 37, Issue 8 https://doi.org/10.1016/j.compositesa.2005.05.030	journal	August 2006
Successful closed-loop recycling of thermoset composites Palmer, J.; Ghita, O. R.; Savage, L. Composites Part A: Applied Science and Manufacturing, Vol. 40, Issue 4 https://doi.org/10.1016/j.compositesa.2009.02.002	journal	April 2009
Kinetic analysis of polydicyclopentadiene oxidation Defauchy, Virginie; Le Gac, Pierre Yves; Guinault, Alain Polymer Degradation and Stability, Vol. 142 https://doi.org/10.1016/j.polymdegradstab.2017.06.005	journal	August 2017
Thermosetting (bio)materials derived from renewable resources: A critical review Raquez, J. -M.; Deléglise, M.; Lacrampe, M. -F. Progress in Polymer Science, Vol. 35, Issue 4 https://doi.org/10.1016/j.progpolymsci.2010.01.001	journal	April 2010
Degradable thermosets based on labile bonds or linkages: A review Ma, Songqi; Webster, Dean C. Progress in Polymer Science, Vol. 76 https://doi.org/10.1016/j.progpolymsci.2017.07.008	journal	January 2018
Cross-Linking Agents for Enhanced Performance of Thermosets Prepared via Frontal Ring-Opening Metathesis Polymerization Ivanoff, Douglas G.; Sung, Jaeuk; Butikofer, Sydney M. Macromolecules, Vol. 53, Issue 19 https://doi.org/10.1021/acs.macromol.0c01530	journal	September 2020
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
Degradable Polyphosphoramidate via Ring-Opening Metathesis Polymerization Liang, Yifei; Sun, Hao; Cao, Wei ACS Macro Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acsmacrolett.0c00401	journal	September 2020
Molecularly Designed Additives for Chemically Deconstructable Thermosets without Compromised Thermomechanical Properties Husted, K. E. L.; Shieh, P.; Lundberg, D. J. ACS Macro Letters, Vol. 10, Issue 7 https://doi.org/10.1021/acsmacrolett.1c00255	journal	June 2021
Cascade Alternating Metathesis Cyclopolymerization of Diynes and Dihydrofuran Sui, Xuelin; Gutekunst, Will R. ACS Macro Letters, Vol. 11, Issue 5 https://doi.org/10.1021/acsmacrolett.2c00140	journal	April 2022
Controlled Alternating Metathesis Copolymerization of Terminal Alkynes Pal, Subhajit; Mandal, Indradip; Kilbinger, Andreas F. M. ACS Macro Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acsmacrolett.2c00258	journal	June 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
Frontal Ring-Opening Metathesis Copolymerization: Deviation of Front Velocity from Mixing Rules Liu, Huiying; Wei, Haibing; Moore, Jeffrey S. ACS Macro Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acsmacrolett.9b00367	journal	June 2019
Degradable Polyacetals/Ketals from Alternating Ring-Opening Metathesis Polymerization Elling, Benjamin R.; Su, Jessica K.; Xia, Yan ACS Macro Letters, Vol. 9, Issue 2 https://doi.org/10.1021/acsmacrolett.9b00936	journal	January 2020
Epoxy Resin/Polyurethane Hybrid Networks Synthesized by Frontal Polymerization Chen, Su; Tian, Yuan; Chen, Li Chemistry of Materials, Vol. 18, Issue 8 https://doi.org/10.1021/cm052391s	journal	March 2006
Plastics Derived from Biological Sources: Present and Future: A Technical and Environmental Review Chen, Guo-Qiang; Patel, Martin K. Chemical Reviews, Vol. 112, Issue 4 https://doi.org/10.1021/cr200162d	journal	December 2011
End Capping Ring-Opening Olefin Metathesis Polymerization Polymers with Vinyl Lactones Hilf, Stefan; Grubbs, Robert H.; Kilbinger, Andreas F. M. Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja8022863	journal	July 2008
Alternating Cascade Metathesis Polymerization of Enynes and Cyclic Enol Ethers with Active Ruthenium Fischer Carbenes Sui, Xuelin; Zhang, Tianqi; Pabarue, Alec B. Journal of the American Chemical Society, Vol. 142, Issue 30 https://doi.org/10.1021/jacs.0c06045	journal	July 2020
Enol Ethers Are Effective Monomers for Ring-Opening Metathesis Polymerization: Synthesis of Degradable and Depolymerizable Poly(2,3-dihydrofuran) Feist, John D.; Xia, Yan Journal of the American Chemical Society, Vol. 142, Issue 3 https://doi.org/10.1021/jacs.9b11834	journal	December 2019
Degradable Cyclooctadiene/Acetal Copolymers: Versatile Precursors to 1,4-Hydroxytelechelic Polybutadiene and Hydroxytelechelic Polyethylene Fraser, Cassandra; Hillmyer, Marc A.; Gutierrez, Elvin Macromolecules, Vol. 28, Issue 21 https://doi.org/10.1021/ma00125a031	journal	October 1995
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
First Synthesis of a Polyurethane by Frontal Polymerization Fiori, Stefano; Mariani, Alberto; Ricco, Laura Macromolecules, Vol. 36, Issue 8 https://doi.org/10.1021/ma0211941	journal	March 2003
UV-Induced Frontal Polymerization of Multifunctional (Meth)acrylates Nason, Charles; Roper, Todd; Hoyle, Charles Macromolecules, Vol. 38, Issue 13 https://doi.org/10.1021/ma048569y	journal	June 2005
Functional Polyolefins Containing Disulfide and Phosphoester Groups: Synthesis and Orthogonal Degradation Chang, Chia-Chih; Emrick, Todd Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma500121a	journal	February 2014
A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization Feist, John D.; Lee, Daniel C.; Xia, Yan Nature Chemistry, Vol. 14, Issue 1 https://doi.org/10.1038/s41557-021-00810-2	journal	November 2021
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
Cleavable comonomers enable degradable, recyclable thermoset plastics Shieh, Peyton; Zhang, Wenxu; Husted, Keith E. L. Nature, Vol. 583, Issue 7817 https://doi.org/10.1038/s41586-020-2495-2	journal	July 2020
A Review on the Potential and Limitations of Recyclable Thermosets for Structural Applications Post, Wouter; Susa, Arijana; Blaauw, Rolf Polymer Reviews, Vol. 60, Issue 2 https://doi.org/10.1080/15583724.2019.1673406	journal	October 2019

Figures / Tables (5)

Similar Records

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Journal Article · Thu Mar 27 00:00:00 EDT 2025 · Angewandte Chemie · OSTI ID:2543100

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Journal Article · Thu Mar 27 00:00:00 EDT 2025 · Angewandte Chemie (International Edition) · OSTI ID:2543138

Related Subjects

36 MATERIALS SCIENCE
3D printing
Materials
Nucleic acid structure
Organic polymers
Plastics

Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Citation Formats

References (38)

Figures / Tables (5)

Similar Records

Related Subjects