Covalent mechanochemistry within bulk polymers typically occurs with irreversible deformation of the parent material. Here we show that embedding mechanophores into an elastomeric poly(dimethylsiloxane) (PDMS) network allows for covalent bond activation under macroscopically reversible deformations. Using the colorimetric mechanophore spiropyran, we show that bond activation can be repeated over multiple cycles of tensile elongation with full shape recovery. Further, localized compression can be used to pattern strain-induced chemistry. The platform enables the reversibility of a secondary strain-induced color change to be characterized. We also observe mechanical acceleration of a flex-activated retro-Diels–Alder reaction, allowing a chemical signal to be released in response to a fully reversible deformation.

Here we present a coumarin dimer (CD) mechanophore that, when embedded near the mid-chain of poly(methyl acrylate) polymers, activates under pulsed ultrasound conditions to yield coumarin chain-end functional polymers. Quantitative photochemical scission of the CD polymers provides a reference against which the activation efficiency of chain-centered mechanophores in polymers synthesized by controlled/living radical polymerization (CRP) can be assessed. Activation efficiency is characterized with respect to the polymer molecular weight (MW), polydispersity index (PDI), and distribution of mechanophores along the backbone.

A primary goal of covalent mechanochemistry is to develop polymer bound mechanophores that undergo constructive transformations in response to otherwise destructive forces. The [2+2] cycloreversion of cyclobutane mechanophores has emerged as a versatile framework to develop a wide range of stress-activated functionality. Herein, we report the development of a class of cyclobutane bearing bicyclo[4.2.0]octane mechanophores. Using carbodiimide polyesterification, these stress-responsive units were incorporated into high molecular weight polymers containing up to 700 mechanophores per polymer chain. Under exposure to the otherwise destructive elongational forces of pulsed ultrasound, these mechanophores unravel by ~7 Å per monomer unit to form α,β-unsaturated esters that react constructively via thiol-ene conjugate addition to form sulfide functionalized copolymers and cross-linked polymer networks. To probe the dynamics of the mechanochemical ring opening, a series of bicyclo[4.2.0]octane derivatives that varied in stereochemistry, substitution, and symmetry were synthesized and activated. Reactivity and product stereochemistry was analyzed by 1H NMR, which allowed us to interrogate the mechanism of the mechanochemical [2+2] cycloreversion. These results support that the ring opening is not concerted, but proceeds via a 1,4 diradical intermediate. The bicyclo[4.2.0]octanes hold promise as active functional groups in new classes of stress-responsive polymeric materials.

The functions of soft robotics are intimately tied to their form-channels and voids defined by an elastomeric superstructure that reversibly stores and releases mechanical energy to change shape, grip objects, and achieve complex motions. Here, we demonstrate that covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation in soft robots into a mechanochromic, covalent chemical response. A bis-alkene functionalized spiropyran (SP) mechanophore is cured into a molded poly(dimethylsiloxane) (PDMS) soft robot walker and gripper. The stresses and strains necessary for SP activation are compatible with soft robot function. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional robotic device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the robot in a way that might be coupled to autonomous feedback loops that allow the robot to regulate its own activity. The demonstration motivates the simultaneous development of new combinations of mechanophores, materials, and soft, active devices for enhanced functionality.