Cross-linker control of vitrimer flow

Bassil M. El-Zaatari; Jacob S.A. Ishibashi; Julia A. Kalow

doi:10.1039/d0py00233j

Cross-linker control of vitrimer flow

Bassil M. El-Zaatari, Jacob S.A. Ishibashi, Julia A. Kalow

Chemistry

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

93 Scopus citations

Abstract

Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition - elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior.

Original language	English (US)
Pages (from-to)	5339-5345
Number of pages	7
Journal	Polymer Chemistry
Volume	11
Issue number	33
DOIs	https://doi.org/10.1039/d0py00233j
State	Published - Sep 7 2020

Funding

The authors gratefully acknowledge the NSF Center for the Chemistry of Molecularly Optimized Networks (NSF CHE-1832256) and a 3M Non-Tenured Faculty Award for funding. This work made use of the Integrated Molecular Structure Education and Research Center at Northwestern, which has received support from the NIH (S10-OD021786-01). Rheological measurements were performed at the Materials Characterization and Imaging Facility which receives support from the MRSEC Program (NSF DMR-1720139) of the Materials Research Center at Northwestern University. The authors additionally thank Dr Scott Danielson, Prof. Michael Rubinstein, and Prof. Stephen Craig (Duke University) for helpful discussion as well as Mukund Kabra for help executing Python code, and Dr John Nardini for help with error analysis.

ASJC Scopus subject areas

Bioengineering
Polymers and Plastics
Biochemistry
Organic Chemistry

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Cite this

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title = "Cross-linker control of vitrimer flow",

abstract = "Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition - elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior.",

author = "El-Zaatari, {Bassil M.} and Ishibashi, {Jacob S.A.} and Kalow, {Julia A.}",

note = "Funding Information: The authors gratefully acknowledge the NSF Center for the Chemistry of Molecularly Optimized Networks (NSF CHE-1832256) and a 3M Non-Tenured Faculty Award for funding. This work made use of the Integrated Molecular Structure Education and Research Center at Northwestern, which has received support from the NIH (S10-OD021786-01). Rheological measurements were performed at the Materials Characterization and Imaging Facility which receives support from the MRSEC Program (NSF DMR-1720139) of the Materials Research Center at Northwestern University. The authors additionally thank Dr Scott Danielson, Prof. Michael Rubinstein, and Prof. Stephen Craig (Duke University) for helpful discussion as well as Mukund Kabra for help executing Python code, and Dr John Nardini for help with error analysis. Publisher Copyright: {\textcopyright} 2020 The Royal Society of Chemistry.",

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AU - El-Zaatari, Bassil M.

AU - Ishibashi, Jacob S.A.

AU - Kalow, Julia A.

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N2 - Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition - elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior.

AB - Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition - elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior.

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Cross-linker control of vitrimer flow

Abstract

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