When one brings "polymeric materials" and "mechanical action" into the same conversation, the topic of this discussion might naturally focus on everyday circumstances such as failure of fibers, fatigue of composites, abrasion of coatings, etc. This intuitive viewpoint reflects the historic consensus in both academia and industry that mechanically induced chemical changes are destructive, leading to polymer degradation that limits materials lifetime on both macroscopic and molecular levels. In the 1930s, Staudinger observed mechanical degradation of polymers, and Melville later discovered that polymer chain scission caused the degradation. Inspired by these historical observations, we sought to redirect the destructive mechanical energy to a productive form that enables mechanoresponsive functions. In this Account, we provide a personal perspective on the origin, barriers, developments, and key advancements of polymer mechanochemistry. We revisit the seminal events that offered molecular-level insights into the mechanochemical behavior of polymers and influenced our thinking. We also highlight the milestones achieved by our group along with the contributions from key comrades at the frontier of this field. We present a workflow for the design, evaluation, and development of new "mechanophores", a term that has come to mean a molecular unit that chemically responds in a selective manner to a mechanical perturbation. We discuss the significance of computation in identifying pairs of points on the mechanophore that promote stretch-induced activation. Attaching polymer chains to the mechanophore at the most sensitive pair and locating the mechanophore near the center of a linear polymer are thought to maximize the efficiency of mechanical-to-chemical energy transduction. We also emphasize the importance of control experiments to validate mechanochemical transformations, both in solution and in the solid state, to differentiate "mechanical" from "thermal" activation. This Account offers our first-hand perspective of the change-in-thinking in polymer mechanochemistry from "destructive" to "productive" and looks at future advances that will stimulate this growing field.

A comb-like dual hydrophilic graft chitosan terpolymer, chitosan grafted with both poly[(2-dimethylamino)ethyl methacrylate] and poly(N-isopropylacrylamide) or, simply, CS(-g-PDMAEMA)-g-PNIPAM, was synthesized by means of atom transfer radical polymerization (ATRP) and click chemistry. At first, PDMAEMA and PNIPAM were synthesized via ATRP, followed by substituting the halide end groups with azido groups. After converting CS into alkynyl-CS via amidation, PDMAEMA-N 3 and PNIPAM-N 3 side chains were successfully grafted onto the CS backbone via click reaction, leading to the well-defined graft terpolymer. Thermo- and pH-responsive micellization behavior of the graft terpolymer in aqueous solutions was investigated by proton nuclear magnetic resonance (1H NMR), laser light scattering (LLS), surface tensiometry, zeta potential, and transmission electron microscopy (TEM). The core−shell structured micelles with PNIAPM as a core and CS/PDMAEMA as a shell were formed in acidic environment (pH < 4) at elevated temperature (>38 °C), whereas the unimers turned into the micelles with CS/PDMAEMA cores in alkaline solutions (pH > 7) at room temperature.

Silica nanoparticles grafted with poly(methyl acrylate) (PMA) chains anchored by a maleimide-anthracene cycloadduct were synthesized to demonstrate mechanochemically selective activation of mechanophores at heterogeneous interfaces. By quantifying the anthracene-containing cleaved PMA polymers, which are generated via retro-[4 + 2] cycloaddition reactions, the first-order kinetic coefficient was determined. Activation characteristics of mechanophores anchored to a nanoparticle exhibit behavior similar to mechanophore-linked polymers, e.g., threshold molecular weight and linear increase in rate coefficient with molecular weight above the threshold. This model system is thus valuable as a probe to test stress activation of interfacially bonded mechanophores relevant to the design of fiber-reinforced polymer composites.

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Encapsulation of actives comprises an area of exploration undergoing rapid growth in both academic and industrial research settings. Encapsulation processes are employed as a part of product synthesis processes for improved efficiency, enhanced stability, active ingredient compatibility, increased safety, targeted delivery, and novel performance of the end product. Such technical benefits enable producers to offer products with increased formulation complexity, access new markets, differentiate products, and improve compatibility and stability, while meeting consumer demands with improved performance, reduced costs, and new actives. In this review, we highlight several emerging academic areas of encapsulation that we believe have specific relevance to industrial formulation, with a focus on three primary areas: supramolecular encapsulation, aqueous self-assembled systems, and emulsion-based capsules. The goal of this review is to help identify the major challenges facing encapsulation technology adoption in the chemical industry, bringing focus and maximizing the potential value of ongoing research efforts.