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

The fracture of rubbery polymer networks involves a series of molecular events, beginning with conformational changes along the polymer backbone and culminating with a chain scission reaction. 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 ( = 5 kDa) with bis-alkyne linkers. Networks were formed under identical conditions, except that the bis-alkyne was varied to include either a -diaryl () or -dialkyl () linked cyclobutane mechanophore that acts as a mechanochemical "weak link" through a force-coupled cycloreversion. A control network featuring a bis-alkyne without cyclobutane () was also synthesized. The networks show the same linear elasticity (' = 23-24 kPa, 0.1-100 Hz) and equilibrium mass swelling ratios ( = 10-11 in tetrahydrofuran), but they exhibit tearing energies that span a factor of 8 (3.4 J, 10.6, and 27.1 J·m for networks with , , and , 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 as a key determinant of the relative ease with which its network is torn. The connection between macroscopic fracture and a small-molecule reaction mechanism suggests opportunities for molecular understanding and optimization of polymer network behavior.