Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange

Keith E.L. Husted; Christopher M. Brown; Peyton Shieh; Ilia Kevlishvili; Samantha L. Kristufek; Hadiqa Zafar; Joseph V. Accardo; Julian C. Cooper; Rebekka S. Klausen; Heather J. Kulik; Jeffrey S. Moore; Nancy R. Sottos; Julia A. Kalow; Jeremiah A. Johnson

doi:10.1021/jacs.2c11858

Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange

Keith E.L. Husted, Christopher M. Brown, Peyton Shieh, Ilia Kevlishvili, Samantha L. Kristufek, Hadiqa Zafar, Joseph V. Accardo, Julian C. Cooper, Rebekka S. Klausen, Heather J. Kulik, Jeffrey S. Moore, Nancy R. Sottos, Julia A. Kalow, Jeremiah A. Johnson^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Convenient strategies for the deconstruction and reprocessing of thermosets could improve the circularity of these materials, but most approaches developed to date do not involve established, high-performance engineering materials. Here, we show that bifunctional silyl ether, i.e., R′O-SiR₂-OR′′, (BSE)-based comonomers generate covalent adaptable network analogues of the industrial thermoset polydicyclopentadiene (pDCPD) through a novel BSE exchange process facilitated by the low-cost food-safe catalyst octanoic acid. Experimental studies and density functional theory calculations suggest an exchange mechanism involving silyl ester intermediates with formation rates that strongly depend on the Si-R₂ substituents. As a result, pDCPD thermosets manufactured with BSE comonomers display temperature- and time-dependent stress relaxation as a function of their substituents. Moreover, bulk remolding of pDCPD thermosets is enabled for the first time. Altogether, this work presents a new approach toward the installation of exchangeable bonds into commercial thermosets and establishes acid-catalyzed BSE exchange as a versatile addition to the toolbox of dynamic covalent chemistry.

Original language	English (US)
Pages (from-to)	1916-1923
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	145
Issue number	3
DOIs	https://doi.org/10.1021/jacs.2c11858
State	Published - Jan 25 2023

Funding

This work was supported by the NSF Center for the Chemistry of Molecularly Optimized Networks (MONET), CHE-2116298. K.E.L.H. acknowledges support from the National Sciences and Engineering Research Council of Canada (for the NSERC PGSD fellowship). C.M.B. acknowledges NSERC for a Postdoctoral Fellowship. H.Z. acknowledges the National Science Foundation Graduate Research Fellowship Grant no. 2141064 for funding. This work used Expanse at San Diego Supercomputing Center through allocation CHE140073 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support (ACCESS) program, which is supported by National Science Foundation Grants #2138259, #2138286, #2138307, #2137603, and #2138296.

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.2c11858

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Husted, K. E. L., Brown, C. M., Shieh, P., Kevlishvili, I., Kristufek, S. L., Zafar, H., Accardo, J. V., Cooper, J. C., Klausen, R. S., Kulik, H. J., Moore, J. S., Sottos, N. R., Kalow, J. A., & Johnson, J. A. (2023). Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange. Journal of the American Chemical Society, 145(3), 1916-1923. https://doi.org/10.1021/jacs.2c11858

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title = "Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange",

abstract = "Convenient strategies for the deconstruction and reprocessing of thermosets could improve the circularity of these materials, but most approaches developed to date do not involve established, high-performance engineering materials. Here, we show that bifunctional silyl ether, i.e., R′O-SiR2-OR′′, (BSE)-based comonomers generate covalent adaptable network analogues of the industrial thermoset polydicyclopentadiene (pDCPD) through a novel BSE exchange process facilitated by the low-cost food-safe catalyst octanoic acid. Experimental studies and density functional theory calculations suggest an exchange mechanism involving silyl ester intermediates with formation rates that strongly depend on the Si-R2 substituents. As a result, pDCPD thermosets manufactured with BSE comonomers display temperature- and time-dependent stress relaxation as a function of their substituents. Moreover, bulk remolding of pDCPD thermosets is enabled for the first time. Altogether, this work presents a new approach toward the installation of exchangeable bonds into commercial thermosets and establishes acid-catalyzed BSE exchange as a versatile addition to the toolbox of dynamic covalent chemistry.",

author = "Husted, {Keith E.L.} and Brown, {Christopher M.} and Peyton Shieh and Ilia Kevlishvili and Kristufek, {Samantha L.} and Hadiqa Zafar and Accardo, {Joseph V.} and Cooper, {Julian C.} and Klausen, {Rebekka S.} and Kulik, {Heather J.} and Moore, {Jeffrey S.} and Sottos, {Nancy R.} and Kalow, {Julia A.} and Johnson, {Jeremiah A.}",

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Husted, KEL, Brown, CM, Shieh, P, Kevlishvili, I, Kristufek, SL, Zafar, H, Accardo, JV, Cooper, JC, Klausen, RS, Kulik, HJ, Moore, JS, Sottos, NR, Kalow, JA & Johnson, JA 2023, 'Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange', Journal of the American Chemical Society, vol. 145, no. 3, pp. 1916-1923. https://doi.org/10.1021/jacs.2c11858

TY - JOUR

T1 - Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange

AU - Husted, Keith E.L.

AU - Brown, Christopher M.

AU - Shieh, Peyton

AU - Kevlishvili, Ilia

AU - Kristufek, Samantha L.

AU - Zafar, Hadiqa

AU - Accardo, Joseph V.

AU - Cooper, Julian C.

AU - Klausen, Rebekka S.

AU - Kulik, Heather J.

AU - Moore, Jeffrey S.

AU - Sottos, Nancy R.

AU - Kalow, Julia A.

AU - Johnson, Jeremiah A.

PY - 2023/1/25

Y1 - 2023/1/25

N2 - Convenient strategies for the deconstruction and reprocessing of thermosets could improve the circularity of these materials, but most approaches developed to date do not involve established, high-performance engineering materials. Here, we show that bifunctional silyl ether, i.e., R′O-SiR2-OR′′, (BSE)-based comonomers generate covalent adaptable network analogues of the industrial thermoset polydicyclopentadiene (pDCPD) through a novel BSE exchange process facilitated by the low-cost food-safe catalyst octanoic acid. Experimental studies and density functional theory calculations suggest an exchange mechanism involving silyl ester intermediates with formation rates that strongly depend on the Si-R2 substituents. As a result, pDCPD thermosets manufactured with BSE comonomers display temperature- and time-dependent stress relaxation as a function of their substituents. Moreover, bulk remolding of pDCPD thermosets is enabled for the first time. Altogether, this work presents a new approach toward the installation of exchangeable bonds into commercial thermosets and establishes acid-catalyzed BSE exchange as a versatile addition to the toolbox of dynamic covalent chemistry.

AB - Convenient strategies for the deconstruction and reprocessing of thermosets could improve the circularity of these materials, but most approaches developed to date do not involve established, high-performance engineering materials. Here, we show that bifunctional silyl ether, i.e., R′O-SiR2-OR′′, (BSE)-based comonomers generate covalent adaptable network analogues of the industrial thermoset polydicyclopentadiene (pDCPD) through a novel BSE exchange process facilitated by the low-cost food-safe catalyst octanoic acid. Experimental studies and density functional theory calculations suggest an exchange mechanism involving silyl ester intermediates with formation rates that strongly depend on the Si-R2 substituents. As a result, pDCPD thermosets manufactured with BSE comonomers display temperature- and time-dependent stress relaxation as a function of their substituents. Moreover, bulk remolding of pDCPD thermosets is enabled for the first time. Altogether, this work presents a new approach toward the installation of exchangeable bonds into commercial thermosets and establishes acid-catalyzed BSE exchange as a versatile addition to the toolbox of dynamic covalent chemistry.

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Remolding and Deconstruction of Industrial Thermosets via Carboxylic Acid-Catalyzed Bifunctional Silyl Ether Exchange

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