This review aims to provide a field guide for the implementation of mechanochemistry in synthetic polymers by summarizing the molecules, materials, and methods that have been developed in this field.
We study the mechanical activation of spiropyran (SP) in a doubly cross-linked polyurethane elastomer. Besides chemical cross-linking, the elastomer comprises polytetrahydrofuran as soft segments and hydrogenbonding 2-ureido-4-pyrimidone (UPy) as hard segments. The material shows two color changes because of the ring-opening reaction of SP to merocyanine (MC) at strained state and the isomerization about the methane bridge of MC at relaxed state. Increasing tensile strain rate leads to stiffer and stronger elastomer as well as earlier activation of SP. The activation point of SP to MC always coincides well with strain hardening of the stress−elongation curves. We further use the two-color transitions of SP to study the fracture of the elastomer during crack propagation.
Directly quantifying a spatially varying stress in soft materials is currently a great challenge. We propose a method to do that by detecting a change in visible light absorption. We incorporate a spiropyran (SP) force–activated mechanophore cross-linker in multiple-network elastomers. The random nature of the network structure of the polymer causes a progressive activation of the SP force probe with load, detectable by the change in color of the material. We first calibrate precisely the chromatic change in uniaxial tension. We then demonstrate that the nominal stress around a loaded crack can be detected for each pixel and that the measured values match quantitatively finite element simulations. This direct method to quantify stresses in soft materials with an internal force probe is an innovative tool that holds great potential to compare quantitatively stresses in different materials with simple optical observations.
A mechanically active spiropyran (SP) mechanophore is incorporated into the backbone of prepolymer which is further end-capped with ureidopyrimidinone (UPy) or urethane. Strong mechanochromic reaction of SP arises in the bulk films of UPy containing materials whereas much weaker activation occurs in urethane containing counterparts, coincident with their stress−strain responses. The difference in the magnitudes of supramolecular interactions leads to different degrees of chain orientation and strain induced crystallization (SIC) in the bulk and consequently distinct capabilities to transfer the load to the mechanophores. This study may aid the design of novel mechanoresponsive materials whose mechanoresponsiveness can be tailored by tuning supramolecular interactions.
The molecular level transfer of stress from a stiff percolating filler to a stretchable matrix is a crucial and generic mechanism of toughening in soft materials.
The diamide–imide
equilibrium was successfully exploited
for the synthesis of dynamic covalent polymer networks in which a
dissociative bond exchange mechanism leads to high processibility
at temperatures above ≈110 °C. Dynamic covalent networks
bridge the gap between thermosets and thermoplastic polymers. At the
operating temperature, when the network is fixed, dynamic covalent
networks are elastic solids, while at high temperatures, chemical
exchange reactions turn the network into a processible viscoelastic
material. Upon heating a dissociative network, the viscosity may also
decrease due to a shift of the chemical equilibrium; in such materials,
the balance between processibility and excessive flow is important.
In this study, a network is prepared that upon heating to above ≈110
°C dissociates to a significant extent due to a shift in the
amide–imide equilibrium of a bisimide, pyromellitic diimide,
in combination with poly(tetrahydrofuran) diamines. At room temperature,
the resulting materials are elastic rubbers with a tensile modulus
of 2–10 MPa, and they become predominantly viscous above a
temperature of approximately 110 °C, which is dependent on the
stoichiometry of the components. The diamide–imide equilibrium
was studied in model reactions with NMR, and variable temperature
infrared (IR) spectroscopy was used to investigate the temperature
dependence of the equilibrium in the network. The temperature-dependent
mechanical properties of the networks were found to be fully reversible,
and the material could be reprocessed several times without loss of
properties such as modulus or strain at break. The high processibility
of these networks at elevated temperatures creates opportunities in
additive manufacturing applications such as selective laser sintering.
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