Polymer Remodeling Enabled by Covalent Mechanochemistry
Material failure is a ubiquitous problem, and it is known that materials fail at much lower stresses than the theoretical maximum calculated from the number and strength of the individual bonds along the material cross-section. The decreased strength is attributed to inhomogeneous stress distributions under load, thus causing the stress to accumulate at localized regions, initiating microcrack formation and subsequent propagation. In many cases, these initiation and propagation steps involve covalent bond scission.
Over the past decade there has been increased interest in channeling the mechanical forces that typically trigger destructive processes (e.g., chain scission) during use into constructive chemical transformations. In an ideal system, these stress-induced chemical transformations would redistribute load prior to material failure, thus extending material lifetime. In this Dissertation, the work of developing constructive transformations through the response of a small molecule "mechanophore" is discussed.
The gem-dihalocyclopropane mechanophore is capable of undergoing a non-scissile electrocyclic ring opening reaction under molecular scale tensile load. The mechanochemistry is demonstrated both in solution via pulsed ultrasound (Chapter 2) and in the bulk via extrusion and uniaxial tension (Chapter 3). In solution, dramatic remodeling at the molecular level occurs under the elongational flow experienced during pulsed ultrasound. Because elongational flow results in regiospecific stress distributions along a polymer main chain, this remodeling converts a gem-dichlorocyclopropane-laden homopolymer into phase separating diblock-copolymers. In the bulk, it is shown that the increased reactivity of an activated gem-dibromocyclopropane mechanophore towards nucleophilic displacement reactions leads to more non-destructive intermolecular bond-forming reactions than chain scissions, indicating the potential of the gem-dibromocyclopropane mechanophore as a self-strengthening platform.
Coupling the idea of mechanophore activation under high forces and covalent bond formation, an autonomous remodeling platform is developed, utilizing the gem-dibromocyclopropane mechanophore and a carboxylate nucleophile (Chapter 4). The system can be either two components, with a mechanophore-based polymer and a small molecule cross-linker, or a one-component system in which the mechanophore and nucleophile are embedded within the same polymer backbone. Both in the bulk and in solution, the autonomous remodeling polymer undergoes mechanophore activation followed by covalent bond formation, creating a cross-linked network in response to high shear forces. This form of remodeling leads to orders of magnitude increases in elastic modulus in response to forces that otherwise degrade polymer molecular weight and material properties. In all cases, the covalent bond formation through nucleophilic displacement of the allylic bromine by a carboxylate is confirmed as the source of polymer remodeling by FTIR as well as numerous control studies.
Together, these studies show that covalent polymer mechanochemistry can be used as a constructive tool for polymer chemistry (the direct conversion of homopolymers into well-ordered diblock copolymers) and materials science (polymers that self-strengthen in response to an applied force). This work paves the way for the future development of new mechanophores that will optimize the proof-of-principle behaviors demonstrated here.
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