Intramolecular Cross‐Linking: Addressing Mechanochemistry with a Bioinspired Approach

Abstract

Many of the attractive properties in polymers are a consequence of their high molecular weight and therefore, scission of chains due to mechanochemistry leads to deterioration in properties and performance. Intramolecular cross-links are systematically added to linear chains, slowing down mechanochemical degradation to the point where the chains become virtually invincible to shear in solution. Our approach mimics the immunoglobulin-like domains of Titin, whose structure directs mechanical force towards the scission of sacrificial intramolecular hydrogen bonds, absorbing mechanical energy while unfolding. The kinetics of the mechanochemical reactions supports this hypothesis, as the polymer properties are maintained while high rates of mechanochemistry are observed. Our results demonstrate that polymers with intramolecular cross-links can be used to make solutions which, even under severe shear, maintain key properties such as viscosity.

Highly Stretchable Polymers: Mechanical Properties Improvement by Balancing Intra‐ and Intermolecular Interactions

“…Folding a polymer chain to a less dynamic structure can be useful in a variety of applications as the macromolecule physical properties and their interactions are significantly affected, while the polymer chemistry remains mostly unchanged . Many studies have characterized SCPN molecular level behavior in solution, in addition to a few melt studies which looked at the interactions between the folded chains . Finally, more recently, we have conducted experimental and theoretical studies to better understand the influence of intramolecular CLs in the solid state, looking at mechanical and thermomechanical behavior of SCPNs assembled into bulk thermoplastic materials .…”

Blavatnik Awards for Young Scientists: K. K. Devaraj, C. E. Diesendruck, and A. L. Goodwin / FCI Dozentenpreise: F. Dielmann, F. Wurm, and B. Morandi

“…Diesendruck's research interests include the effect of mechanical stress in macromolecules, as well as the chemical decomposition of cations in alkaline fuel‐cell membranes and the development of new ionomers with enhanced stability. He has reported the European Journal of Organic Chemistry on the olefination of N ‐sulfinylimines under mild conditions, and in Angewandte Chemie on the introduction of molecular cross‐links to molecular polymers . He is the Associate Editor of the Israel Journal of Chemistry .…”

Blavatnik‐Preise für junge Wissen‐ schaftler: N. K. Devaraj, C. E. Diesendruck und A. L. Goodwin / FCI‐Dozentenpreise: F. Dielmann, F. Wurm und B. Morandi

“…Diesendruck untersucht den Einfluss von mechanischen Reizen auf Makromoleküle und die chemische Abscheidung von Kationen in den Membranen alkalischer Brennstoffzellen, und er entwickelt neue Ionomere mit verbesserter Stabilität. Im European Journal of Organic Chemistry hatte er einen Beitrag über die milde Olefinierung von N ‐Sulfinyliminen, und in der Angewandten Chemie berichtete er über die Einführung intramolekularer Vernetzungen in Polymere . Er ist Associate Editor des Israel Journal of Chemistry .…”