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FractureTransitionState-ChemRxiv.pdf (1.96 MB)

Mechanism Dictates Mechanics: A Molecular Substituent Effect in the Macroscopic Fracture of a Covalent Polymer Network

preprint
submitted on 09.01.2021, 04:07 and posted on 11.01.2021, 12:37 by Shu Wang, Haley Beech, Brandon Bowser, Tatiana Kouznetsova, Bradley Olsen, Michael Rubinstein, Stephen Craig

Here, we report covalent polymer gels in which the macroscopic fracture “reaction” is controlled by mechanophores embedded within mechanically active network strands. We synthesized poly(ethylene glycol) (PEG) gels through the end-linking of azide-terminated tetra-arm PEG (Mn = 5 kDa) with bis-alkyne linkers. Networks were formed under identical conditions, except that the bis-alkyne was varied to include either a cis-diaryl (1) or cis-dialkyl (2) linked cyclobutane mechanophore that acts as a mechanochemical “weak link” through a force-coupled cycloreversion. A control network featuring a bis-alkyne without cyclobutane (3) was also synthesized. The networks show the same linear elasticity (G' = 23~24 kPa, 0.1 – 100 Hz) and equilibrium mass swelling ratios (Q = 10~11 in tetrahydrofuran), but they exhibit tearing energies that span a factor of 8 (3.4 J∙m-2, 10.5 J∙m-2, and 27.1 J∙m-2 for networks with 1, 2, and 3, respectively). The difference in fracture energy is well aligned with the force-coupled scission kinetics of the mechanophores observed in single-molecule force spectroscopy experiments, implicating local resonance stabilization of a diradical transition state in the cycloreversion of 1 as a key determinant of the relative ease with which its network is torn. The connection between macroscopic fracture and small molecule reaction mechanism suggests opportunities for molecular understanding and optimization of polymer network behavior.

Funding

CHE-1832256

History

Email Address of Submitting Author

stephen.craig@duke.edu

Institution

Duke University

Country

United State

ORCID For Submitting Author

0000-0002-8810-0369

Declaration of Conflict of Interest

No conflict of interest

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