Title: Tuning the Mechanical and Dynamic Properties of Elastic Vitrimers by Tailoring the Substituents of Boronic Ester

Abstract

Elastic vitrimers, i.e., elastic polymers with associative dynamic covalent bonds, can afford elastomers with recyclability while maintaining their thermal and chemical stability. Herein, we report a series of boronic ester-based vitrimers with tunable mechanical properties and recyclability by varying the substitute groups of boronic acid in polymer networks. The dynamic polymer networks are formed by reacting diol-containing tetra-arm poly(amidoamine) with boronic acid-terminated tetra-arm poly(ethylene glycol), which possesses different substituents adjacent to boronic acid moieties. Varying the substituent adjacent to the boronic ester unit will significantly affect the binding strength of the boronic ester, therefore affecting their dynamics and mechanical performance. The electron-withdrawing substituents noticeably suppress the dynamics of boronic ester exchange and increase the activation energy and relaxation time while enhancing the mechanical strength of the resulting elastic vitrimers. On the other hand, the presence of electron-rich substituent affords relatively reduced glass transition temperature (T_g), faster relaxation, and prominent recyclability and malleability at lower temperatures. The developed pathway will guide the rational design of elastomers with well-tunable dynamics and processabilities.

Authors:

Demchuk, Zoriana ^[1]; Zhao, Xiao ^[1]; Shen, Zhiqiang ^[2]; Zhao, Sheng ^[3]; Sokolov, Alexei P.  ^[4];

• Search DOE PAGES for author "Sokolov, Alexei P."
• Search DOE PAGES for ORCID "0000-0002-8187-9445"

Cao, Peng-Fei  ^[5]

• Search DOE PAGES for author "Cao, Peng-Fei"
• Search DOE PAGES for ORCID "0000-0003-2391-1838"

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+ Show Author Affiliations

1. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
2. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States
3. Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
4. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States, Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
5. State Key Laboratory of Organic–Inorganic Composites, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Publication Date:

Fri Dec 29 00:00:00 EST 2023

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Beijing University of Chemical Technology (China)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Building Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

2267596

Alternate Identifier(s):

OSTI ID: 2281094; OSTI ID: 2323454

Grant/Contract Number:  

AC05-00OR22725

Resource Type:

Published Article

Journal Name:

ACS Materials Au

Additional Journal Information:

Journal Name: ACS Materials Au Journal Volume: 4 Journal Issue: 2; Journal ID: ISSN 2694-2461

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

elastic vitrimer; dynamic covalent bond; binding strength; tunable dynamics; recycled elastomer; alcohols; nucleic acid structure; organic compounds; polymers; substituents; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE