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Abstract Polymer networks containing dynamic covalent bonds do not exhibit traditional thermoset material properties. Such dynamic covalent networks have the ability to undergo stress relaxation processes associated with dynamic covalent bond exchange, imparting these materials with adaptive/responsive properties. Reported herein is an investigation on the effect that changing the amount of dynamic hindered alkylurea bonds has on the viscoelastic behavior of a series of poly(alkylurea‐
co ‐urethane) networks prepared by reacting a trifunctional isocyanate crosslinker with varying ratios of anN ‐isopropyl amine endcapped poly(propylene glycol) and a poly(propylene glycol). Films that contain >50% dynamic alkylurea bonds (wrt. alkylurea + urethane bonds) exhibit facile reprocessability, while those films with <50% dynamic alkylurea bonds exhibit poor reprocessability under these same conditions. Analysis of the temperature‐dependent shear rheometry and uniaxial stress relaxation measurements demonstrates that the primary stress relaxation mode in these materials is linked to the dynamic bond exchange process. Interestingly, these films exhibit an increasingly rich viscoelastic spectrum with increasing fraction of non‐dynamic urethane bonds. In addition to the primary relaxation process an order‐of‐magnitude slower relaxation emerges, which is identified as being related to the relaxation of larger, permanently crosslinked polymeric clusters in an otherwise dynamic matrix. -
Abstract Mechano‐activated chemistry is a powerful tool for remodeling of synthetic polymeric materials, however, few reactions are currently available. Here we show that using piezochemical reduction of a CuII‐based pre‐catalyst, a step‐growth polymerization occurs via the copper catalyzed azide–alkyne cycloaddition (CuAAC) reaction to form a linear polytriazole. Furthermore, we show that a linear polymer can be crosslinked mechanochemically using the same chemistry to form a solid organogel. We envision that this chemistry can be used to harness mechanical energy for constructive purposes in polymeric materials.
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Abstract Mechano‐activated chemistry is a powerful tool for remodeling of synthetic polymeric materials, however, few reactions are currently available. Here we show that using piezochemical reduction of a CuII‐based pre‐catalyst, a step‐growth polymerization occurs via the copper catalyzed azide–alkyne cycloaddition (CuAAC) reaction to form a linear polytriazole. Furthermore, we show that a linear polymer can be crosslinked mechanochemically using the same chemistry to form a solid organogel. We envision that this chemistry can be used to harness mechanical energy for constructive purposes in polymeric materials.