Effect of strand molecular length on mechanochemical transduction in elastomers probed with uniform force sensors. Issue 14 (20th March 2023)

• Record Type: Journal Article
• Authors: Ouchi, Tetsu; Wang, Wencong; Silverstein, Brooke E.; Johnson, Jeremiah A.; Craig, Stephen L.
• Is Part Of: Polymer chemistry. Volume 14:Issue 14(2023)
• Page Start: 1646
• Page End: 1655
• Publication Date: 2023-03-20
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/d3py00065f
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : The impact of strand molecular length on mechanical response is elucidated through the incorporation of uniform mechanochromic force probes. Abstract : The mechanical properties of a polymer network reflect the collective behavior of all of the constituent strands within the network. These strands comprise a distribution of states, and a central question is how the deformation and tension experienced by a strand is influenced by strand length. Here, we address this question through the use of mechanophore force probes with discrete molecular weights. Probe strands, each bearing a mechanochromic spiropyran (SP), were prepared through an iterative synthetic strategy, providing uniform PDMS-functionalized SP force probes with molecular weights of 578, 1170, and 2356 g mol −1 . The probes were each doped (9 mM) into the same silicone elastomer matrix. Upon stretching, the materials change color, consistent with the expected conversion of SP to merocyanine (MC). The critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but it is independent of the molecular length of the probe strand. When a network with activated strands is relaxed, the color dissipates, and the rate of decoloration varies as a function of the relaxing strain (  r ); faster decoloration occurs at lower  r . The dependence of decoloration rate on  r is taken to reflect the effect of residual tension in the once-activated strands on the reversion reaction of MC to SP, and the effect of that residual tension is indistinguishable across the three molecular lengths examined. The combination of discrete strand synthesis and mechanochromism provides a foundation to further test and develop molecular-based theories of elasticity and fracture in polymer networks.