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

Zhang, Shuyi; Xu, Zhenchuang; Husted, Keith E. L.; Lundberg, David J.; Brown, Christopher M.; Wang, Yuyan; Shieh, Peyton; Ko, Kwangwook; Moore, Jeffrey S.; Johnson, Jeremiah A.

doi:10.1002/anie.202500104

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)

DOI:https://doi.org/10.1002/anie.202500104· OSTI ID:2543138

Zhang, Shuyi ^[1]; Xu, Zhenchuang ^[2]; Husted, Keith E. L. ^[1]; Lundberg, David J. ^[3]; Brown, Christopher M. ^[1]; Wang, Yuyan ^[1]; Shieh, Peyton ^[1]; Ko, Kwangwook ^[1]; Moore, Jeffrey S. ^[2]; ^[1]

Department of Chemistry Massachusetts Institute of Technology Cambridge Massachusetts 02139 USA
Beckman Institute for Advanced Science and Technology University of Illinois at Urbana–Champaign Urbana Illinois 61801 USA, Department of Chemistry University of Illinois at Urbana–Champaign Urbana Illinois 61801 USA
Department of Chemical Engineering Massachusetts Institutes of Technology Cambridge Massachusetts 02139 USA

Abstract

Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands of thermosets using cleavable comonomers as additives can facilitate thermoset deconstruction without replacement of permanent cross‐links, but such monomers can lead to reduced thermomechanical properties and require high loadings to function effectively, motivating the design of new and optimal cleavable additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which fuse two network strands via a four‐way cleavable cross‐link. SFCs enable deconstruction of model polydicyclopentadiene (pDCPD) thermosets with as little as one‐fifth of the molar loading needed to achieve deconstruction using traditional cleavable comonomers. SFCs function under traditional oven curing as well as low‐energy frontal ring‐opening metathesis polymerization (FROMP) conditions and lead to improved thermomechanical properties, for example, glass transition temperatures, compared to prior cleavable comonomer designs. This work motivates the development of increasingly improved cleavable additives to enable thermoset deconstruction without compromising material performance.

View Journal Article

Sponsoring Organization:: USDOE

OSTI ID:: 2543138

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 19 Vol. 64; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (61)

Studies of crosslinked styrene-alkyl acrylate copolymers for oil absorbency application. I. Synthesis and characterization Jang, Jyongsik; Kim, Beom-Seok Journal of Applied Polymer Science, Vol. 77, Issue 4 https://doi.org/10.1002/(SICI)1097-4628(20000725)77:4<903::AID-APP26>3.0.CO;2-E	journal	July 2000
Polydimethylsiloxane (PDMS): Environmental Fate and Effects Fendinger, Nicholas J. Organosilicon Chemistry Set: From Molecules to Materials https://doi.org/10.1002/9783527620777.ch103c	book	January 2008
Perspectives in the Development of High‐Temperature Polymers Hergenrother, Paul M. Angewandte Chemie International Edition in English, Vol. 29, Issue 11 https://doi.org/10.1002/anie.199012621	journal	November 1990
Molecular structure and physical properties of E‐beam crosslinked low‐density polyethylene for wire and cable insulation applications Dadbin, Susan; Frounchi, Masoud; Saeid, M. Haji Journal of Applied Polymer Science, Vol. 86, Issue 8 https://doi.org/10.1002/app.11111	journal	September 2002
Polydicyclopentadiene based aerogel: a new insulation material Lee, Je Kyun; Gould, George L. Journal of Sol-Gel Science and Technology, Vol. 44, Issue 1 https://doi.org/10.1007/s10971-007-1598-7	journal	July 2007
The use of thermosets in modern aerospace applications Hamerton, I.; Kratz, J. https://doi.org/10.1016/B978-0-08-101021-1.00009-5	book	January 2018
Biomolecule-sensitive hydrogels Miyata, Takashi; Uragami, Tadashi; Nakamae, Katsuhiko Advanced Drug Delivery Reviews, Vol. 54, Issue 1 https://doi.org/10.1016/S0169-409X(01)00241-1	journal	January 2002
Reaction: Polymer Chemistries Enabling Cradle-to-Cradle Life Cycles for Plastics Helms, Brett A.; Russell, Thomas P. Chem, Vol. 1, Issue 6 https://doi.org/10.1016/j.chempr.2016.11.016	journal	December 2016
Epoxy clay nanocomposites – processing, properties and applications: A review Azeez, Asif Abdul; Rhee, Kyong Yop; Park, Soo Jin Composites Part B: Engineering, Vol. 45, Issue 1 https://doi.org/10.1016/j.compositesb.2012.04.012	journal	February 2013
Synthesis and application of epoxy resins: A review Jin, Fan-Long; Li, Xiang; Park, Soo-Jin Journal of Industrial and Engineering Chemistry, Vol. 29 https://doi.org/10.1016/j.jiec.2015.03.026	journal	September 2015
The effect of nanoparticles on the adhesion of epoxy adhesive Zhai, Lanlan; Ling, Guoping; Li, Jian Materials Letters, Vol. 60, Issue 25-26 https://doi.org/10.1016/j.matlet.2006.02.038	journal	November 2006
Malleable and Recyclable Thermosets: The Next Generation of Plastics Jin, Yinghua; Lei, Zepeng; Taynton, Philip Matter, Vol. 1, Issue 6 https://doi.org/10.1016/j.matt.2019.09.004	journal	December 2019
Durability of polydicyclopentadiene under high temperature, high pressure and seawater (offshore oil production conditions) Le Gac, P. Y.; Choqueuse, D.; Paris, M. Polymer Degradation and Stability, Vol. 98, Issue 3 https://doi.org/10.1016/j.polymdegradstab.2012.12.023	journal	March 2013
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
Methods for polyurethane and polyurethane composites, recycling and recovery: A review Zia, Khalid Mahmood; Bhatti, Haq Nawaz; Ahmad Bhatti, Ijaz Reactive and Functional Polymers, Vol. 67, Issue 8 https://doi.org/10.1016/j.reactfunctpolym.2007.05.004	journal	August 2007
Dramatic Toughness Enhancement of Polydicyclopentadiene Composites by Incorporating Low Amounts of Vinyl-Functionalized SiO₂ Wang, Yaqi; Zhang, Li; Sun, Jiacheng Industrial & Engineering Chemistry Research, Vol. 56, Issue 16 https://doi.org/10.1021/acs.iecr.7b00093	journal	April 2017
Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms Lundberg, David J.; Kilgallon, Landon J.; Cooper, Julian C. Macromolecules, Vol. 57, Issue 14 https://doi.org/10.1021/acs.macromol.4c00835	journal	July 2024
50th Anniversary Perspective : There Is a Great Future in Sustainable Polymers Schneiderman, Deborah K.; Hillmyer, Marc A. Macromolecules, Vol. 50, Issue 10 https://doi.org/10.1021/acs.macromol.7b00293	journal	May 2017
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
Production and Dynamic Mechanical Analysis of Macro-Scale Functionalized Polydicyclopentadiene Objects Facilitated by Rational Synthesis and Reaction Injection Molding Cuthbert, Tyler J.; Li, Tong; Wulff, Jeremy E. ACS Applied Polymer Materials, Vol. 1, Issue 9 https://doi.org/10.1021/acsapm.9b00571	journal	August 2019
Reprocessing Postconsumer Polyurethane Foam Using Carbamate Exchange Catalysis and Twin-Screw Extrusion Sheppard, Daylan T.; Jin, Kailong; Hamachi, Leslie S. ACS Central Science, Vol. 6, Issue 6 https://doi.org/10.1021/acscentsci.0c00083	journal	April 2020
Reprocessable Cross-Linked Polymer Networks: Are Associative Exchange Mechanisms Desirable? Elling, Benjamin R.; Dichtel, William R. ACS Central Science, Vol. 6, Issue 9 https://doi.org/10.1021/acscentsci.0c00567	journal	July 2020
A Model Ensemble Approach Enables Data-Driven Property Prediction for Chemically Deconstructable Thermosets in the Low-Data Regime AlFaraj, Yasmeen S.; Mohapatra, Somesh; Shieh, Peyton ACS Central Science, Vol. 9, Issue 9 https://doi.org/10.1021/acscentsci.3c00502	journal	September 2023
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
Catalytic Control of Plastic Flow in Siloxane-Based Liquid Crystalline Elastomer Networks Saed, Mohand O.; Terentjev, Eugene M. ACS Macro Letters, Vol. 9, Issue 5 https://doi.org/10.1021/acsmacrolett.0c00265	journal	May 2020
Topological Polymer Chemistry Enters Materials Science: Expanding the Applicability of Cyclic Polymers Romio, Matteo; Trachsel, Lucca; Morgese, Giulia ACS Macro Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acsmacrolett.0c00358	journal	June 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
Controllable Degradation of Polyurethane Thermosets with Silaketal Linkages in Response to Weak Acid Zhang, Shoupeng; Xu, Xiao-Qi; Liao, Shenglong ACS Macro Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acsmacrolett.2c00204	journal	June 2022
Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives Lundberg, David J.; Ko, Kwangwook; Kilgallon, Landon J. ACS Macro Letters, Vol. 13, Issue 5 https://doi.org/10.1021/acsmacrolett.4c00106	journal	April 2024
Chemically Recyclable Biobased Polyurethanes Schneiderman, Deborah K.; Vanderlaan, Marie E.; Mannion, Alexander M. ACS Macro Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsmacrolett.6b00193	journal	March 2016
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
Brønsted-Acid-Catalyzed Exchange in Polyester Dynamic Covalent Networks Self, Jeffrey L.; Dolinski, Neil D.; Zayas, Manuel S. ACS Macro Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acsmacrolett.8b00370	journal	June 2018
Thermally Crosslinked Functionalized Polydicyclopentadiene with a High T_g and Tunable Surface Energy Chen, Jun; Burns, Fraser P.; Moffitt, Matthew G. ACS Omega, Vol. 1, Issue 4 https://doi.org/10.1021/acsomega.6b00193	journal	October 2016
DNA-Crosslinked 2D Photonic Crystal Hydrogels for Detection of Adenosine Actuated by an Adenosine-Binding Aptamer Jang, Kyeongwoo; Westbay, James H.; Asher, Sanford A. ACS Sensors, Vol. 7, Issue 6 https://doi.org/10.1021/acssensors.1c02424	journal	May 2022
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
Some Interesting Things about Polysiloxanes Mark, James E. Accounts of Chemical Research, Vol. 37, Issue 12 https://doi.org/10.1021/ar030279z	journal	December 2004
Chemical Stress-Relaxation of Polydimethylsiloxane Elastomers ¹ Osthoff, R. C.; Bueche, A. M.; Grubb, W. T. Journal of the American Chemical Society, Vol. 76, Issue 18 https://doi.org/10.1021/ja01647a052	journal	September 1954
Molecular Size Distribution in Three Dimensional Polymers. I. Gelation ¹ Flory, Paul J. Journal of the American Chemical Society, Vol. 63, Issue 11 https://doi.org/10.1021/ja01856a061	journal	November 1941
A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism Zheng, Peiwen; McCarthy, Thomas J. Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja2113257	journal	January 2012
Cleavable Comonomers for Chemically Recyclable Polystyrene: A General Approach to Vinyl Polymer Circularity Kiel, Gavin R.; Lundberg, David J.; Prince, Elisabeth Journal of the American Chemical Society, Vol. 144, Issue 28 https://doi.org/10.1021/jacs.2c05374	journal	June 2022
Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange Husted, Keith E. L.; Brown, Christopher M.; Shieh, Peyton Journal of the American Chemical Society, Vol. 145, Issue 3 https://doi.org/10.1021/jacs.2c11858	journal	January 2023
Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C–N Bonds Obadia, Mona M.; Mudraboyina, Bhanu P.; Serghei, Anatoli Journal of the American Chemical Society, Vol. 137, Issue 18 https://doi.org/10.1021/jacs.5b02653	journal	April 2015
A New Derivation of Average Molecular Weights of Nonlinear Polymers Macosko, Christopher W.; Miller, Douglas R. Macromolecules, Vol. 9, Issue 2 https://doi.org/10.1021/ma60050a003	journal	March 1976
Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone Hong, Miao; Chen, Eugene Y. -X. Nature Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/nchem.2391	journal	November 2015
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
Strategies to reduce the global carbon footprint of plastics Zheng, Jiajia; Suh, Sangwon Nature Climate Change, Vol. 9, Issue 5 https://doi.org/10.1038/s41558-019-0459-z	journal	April 2019
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
Siloxane crosslinks with dynamic bond exchange enable shape programming in liquid-crystalline elastomers Saed, Mohand O.; Terentjev, Eugene M. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-63508-4	journal	April 2020
Plastic upcycling No authors listed Nature Catalysis, Vol. 2, Issue 11, p. 945-946 https://doi.org/10.1038/s41929-019-0391-7	journal	November 2019
Designing degradable hydrogels for orthogonal control of cell microenvironments Kharkar, Prathamesh M.; Kiick, Kristi L.; Kloxin, April M. Chem. Soc. Rev., Vol. 42, Issue 17 https://doi.org/10.1039/C3CS60040H	journal	April 2013
Modified biopolymer-dextrin based crosslinked hydrogels: application in controlled drug delivery Das, Dipankar; Pal, Sagar RSC Advances, Vol. 5, Issue 32 https://doi.org/10.1039/C4RA16103C	journal	January 2015
Polyurethane types, synthesis and applications – a review Akindoyo, John O.; Beg, M. D. H.; Ghazali, Suriati RSC Advances, Vol. 6, Issue 115 https://doi.org/10.1039/C6RA14525F	journal	January 2016
Harnessing the surface chemistry of methyl ester functionalized polydicyclopentadiene and exploring surface bioactivity Li, Tong; Shumka, Hannah; Cuthbert, Tyler J. Materials Advances, Vol. 1, Issue 6 https://doi.org/10.1039/D0MA00480D	journal	January 2020
Orthogonally deconstructable and depolymerizable polysilylethers via entropy-driven ring-opening metathesis polymerization Johnson, Alayna M.; Husted, Keith E. L.; Kilgallon, Landon J. Chemical Communications, Vol. 58, Issue 61 https://doi.org/10.1039/D2CC02718F	journal	January 2022
A Critical Review: The Modification, Properties, and Applications of Epoxy Resins Mohan, Pragyan Polymer-Plastics Technology and Engineering, Vol. 52, Issue 2 https://doi.org/10.1080/03602559.2012.727057	journal	January 2013
Plastics: friends or foes? The circularity and plastic waste footprint Klemeš, Jiří Jaromír; Fan, Yee Van; Jiang, Peng Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, Vol. 43, Issue 13 https://doi.org/10.1080/15567036.2020.1801906	journal	August 2020
Production, use, and fate of all plastics ever made Geyer, Roland; Jambeck, Jenna R.; Law, Kara Lavender Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700782	journal	July 2017
Toward Recyclable Thermosets Long, Timothy E. Science, Vol. 344, Issue 6185 https://doi.org/10.1126/science.1254401	journal	May 2014
Evaluating scenarios toward zero plastic pollution Lau, Winnie W. Y.; Shiran, Yonathan; Bailey, Richard M. Science, Vol. 369, Issue 6510 https://doi.org/10.1126/science.aba9475	journal	July 2020
Hydrolysis and Solvolysis as Benign Routes for the End-of-Life Management of Thermoset Polymer Waste Shen, Minjie; Cao, Hongda; Robertson, Megan L. Annual Review of Chemical and Biomolecular Engineering, Vol. 11, Issue 1 https://doi.org/10.1146/annurev-chembioeng-120919-012253	journal	June 2020

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

Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction

Journal Article · Wed Sep 21 00:00:00 EDT 2022 · Chemistry of Materials · OSTI ID:2370403

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

Citation Formats

References (61)

Similar Records

Related Subjects