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NameMr. Joshua Marquez
EmailEmail hidden; Javascript is required.
OrganizationUniversity of Florida
PositionGraduate Student
InvitedNo
TypePoster
TopicPMSE/POLY
Title

Electrochemically Functionalizing Macromolecules

Author(s)

Joshua D. Marquez, Rhys W. Hughes, James B. Young, Austin M. Evans,* and Brent S. Sumerlin*

Author Location(s)

University of Florida

Abstract

Electrochemical methodologies are powerful for the creation and destruction of challenging
chemical functionality. The deployment of these methodologies on macromolecular substrates is
underexplored. We have recently shown that polymers containing N-(acryloxy)phthalimides could be subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. In the presence of an H-atom donor, poly(N-(acryloxy)phthalimide-co-methyl methacrylate) copolymers subjected to these electrolysis conditions produced poly(ethylene-co-methyl acrylate) and poly(propylene-co-methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. In the absence of an H-atom donor, electrochemical decarboxylation degraded all-methacrylate poly(N(methacryloxy)phthalimide -co-methyl
methacrylate) copolymers with a degradation efficiency of >95% through a β-scission process.
While decarboxylating N-(acyloxy)phthalimides is electrochemically efficient; it leads to significant
mass loss and low atom economies. We have now demonstrated how direct decarboxylation from
poly(acrylic acid) can also yield polyolefins in the presence of an H-atom donor. By using
poly(methyl acrylate-b-acrylic acid), poly(butyl acrylate-b-acrylic acid), and poly(styrene-b-acrylic acid) precursors, block-polyolefins are generated after electrochemical modification, which are challenging to prepare through other methods. Spectroscopic and chromatographic techniques reveal that these transformations are near-quantitative. Electrochemistry is thus shown to be a powerful tool in selective polymer transformations and controlled macromolecular degradation without the need for activated ester handles.

Date06/01/2024