On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

Lorelis González-López, Logan Kearney, Christopher J. Janke, James Wishart, Nihal Kanbargi, Mohamad Al-Sheikhly

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

Original languageEnglish
Article number803347
JournalFrontiers in Chemistry
Volume9
DOIs
StatePublished - Jan 11 2022

Funding

JW thanks Bobby Layne for assistance with the gamma irradiations. Financial support of the Oakridge National Laboratory by the U.S. DOE under contract DE-AC05-00OR22725, is gratefully acknowledged. The work at BNL and use of the 60Co gamma source of the BNL Accelerator Center for Energy Research was supported by the U.S. DOE Office of Science, Division of Chemical Sciences, Geosciences and Biosciences under contract DESC0012704.

Keywords

  • EPR spectroscopy
  • gamma radiolysis
  • polymer degradation
  • polymer networks
  • unsaturated polyester resins

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