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Title: Tailoring Lifetimes and Properties of Carbodiimide-Fueled Covalently Cross-linked Polymer Networks

Abstract

The mechanical properties of nonequilibrium polymer hydrogels obtained from the transient cross-linking of polymer chains by a chemical fuel were investigated. Aqueous polymers featuring pendant carboxylic acids were treated with a carbodiimide to give anhydride-cross-linked gels. The anhydrides spontaneously hydrolyze back to the polymer solution, and the cycle can be repeated multiple times. Oscillatory rheology was employed to study the effects of temperature, fuel concentration, chain length, and polymer composition on the storage and loss moduli of the polymeric materials as well as the time taken for the polymers to undergo decross-linking. Regardless of the temperature used, at constant carbodiimide concentration, degelation times are more sensitive to experimental temperature than are the peak storage moduli. Decross-linking times decrease with increasing temperature. As carbodiimide concentration decreases, there is a decrease in moduli and decross-linking times. Within the scope of materials studied, the polymer structure was found to have a relatively small impact on the transient properties of gel networks compared to the fuel concentration and temperature. Furthermore, these findings facilitate the design of tunable on-demand networks and gels.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Miami Univ., Oxford, OH (United States)
Publication Date:
Research Org.:
Miami Univ., Oxford, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1879882
Grant/Contract Number:  
SC0018645; DMR-1749730; CHE-1851795; CHE-1919850
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 54; Journal Issue: 21; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nonequilibrium assembly; polymer networks; carbodiimides; dissipative assembly; fuels; hydrolysis; nucleic acid structure; polymer solutions; polymers

Citation Formats

Dodo, Obed J., Petit, Leilah, Rajawasam, Chamoni W. H., Hartley, C. Scott, and Konkolewicz, Dominik. Tailoring Lifetimes and Properties of Carbodiimide-Fueled Covalently Cross-linked Polymer Networks. United States: N. p., 2021. Web. doi:10.1021/acs.macromol.1c01586.
Dodo, Obed J., Petit, Leilah, Rajawasam, Chamoni W. H., Hartley, C. Scott, & Konkolewicz, Dominik. Tailoring Lifetimes and Properties of Carbodiimide-Fueled Covalently Cross-linked Polymer Networks. United States. https://doi.org/10.1021/acs.macromol.1c01586
Dodo, Obed J., Petit, Leilah, Rajawasam, Chamoni W. H., Hartley, C. Scott, and Konkolewicz, Dominik. Tue . "Tailoring Lifetimes and Properties of Carbodiimide-Fueled Covalently Cross-linked Polymer Networks". United States. https://doi.org/10.1021/acs.macromol.1c01586. https://www.osti.gov/servlets/purl/1879882.
@article{osti_1879882,
title = {Tailoring Lifetimes and Properties of Carbodiimide-Fueled Covalently Cross-linked Polymer Networks},
author = {Dodo, Obed J. and Petit, Leilah and Rajawasam, Chamoni W. H. and Hartley, C. Scott and Konkolewicz, Dominik},
abstractNote = {The mechanical properties of nonequilibrium polymer hydrogels obtained from the transient cross-linking of polymer chains by a chemical fuel were investigated. Aqueous polymers featuring pendant carboxylic acids were treated with a carbodiimide to give anhydride-cross-linked gels. The anhydrides spontaneously hydrolyze back to the polymer solution, and the cycle can be repeated multiple times. Oscillatory rheology was employed to study the effects of temperature, fuel concentration, chain length, and polymer composition on the storage and loss moduli of the polymeric materials as well as the time taken for the polymers to undergo decross-linking. Regardless of the temperature used, at constant carbodiimide concentration, degelation times are more sensitive to experimental temperature than are the peak storage moduli. Decross-linking times decrease with increasing temperature. As carbodiimide concentration decreases, there is a decrease in moduli and decross-linking times. Within the scope of materials studied, the polymer structure was found to have a relatively small impact on the transient properties of gel networks compared to the fuel concentration and temperature. Furthermore, these findings facilitate the design of tunable on-demand networks and gels.},
doi = {10.1021/acs.macromol.1c01586},
journal = {Macromolecules},
number = 21,
volume = 54,
place = {United States},
year = {2021},
month = {10}
}

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