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.

Highlights

  • Unsaturated polyester resins (UPRs) represent a high-volume class of thermoset materials used in a wide range of coatings, adhesives, and composite applications. (Delahaye et al, 1998; Dholakiya, 2012) These characteristic ester bond-containing reactants can be combined with a myriad of additives to produce a system exhibiting broadly tunable physical and chemical property sets. (Sanchez et al, 2000) Rigidity, thermal stability and chemical resistance are critical design factors and are moderated through the use of various monomers, additives and sub-unit moieties that alter the free volume, glass transitions and chemical interactions

  • Gamma Radiolysis for Recycling of Polyester Resins et al, 2019) Network formation occurs via the free radical initiated polymerization of the monomer additive, which crosslinks with the unsaturated portions of the chain backbone. (Long, 2014) UPRs can be roughly categorized by the main reactant combinations that largely determine the characteristics of the materials and their optimal application

  • This signal is characteristic of the alkoxyl radicals formed after γ radiolysis of the DCPD resin in DMSO, isopropyl alcohol (IPA), and H2O

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Summary

Introduction

Unsaturated polyester resins (UPRs) represent a high-volume class of thermoset materials used in a wide range of coatings, adhesives, and composite applications. (Delahaye et al, 1998; Dholakiya, 2012) These characteristic ester bond-containing reactants can be combined with a myriad of additives to produce a system exhibiting broadly tunable physical and chemical property sets. (Sanchez et al, 2000) Rigidity, thermal stability and chemical resistance are critical design factors and are moderated through the use of various monomers, additives and sub-unit moieties that alter the free volume, glass transitions and chemical interactions. Unsaturated polyester resins (UPRs) represent a high-volume class of thermoset materials used in a wide range of coatings, adhesives, and composite applications. (Sanchez et al, 2000) Rigidity, thermal stability and chemical resistance are critical design factors and are moderated through the use of various monomers, additives and sub-unit moieties that alter the free volume, glass transitions and chemical interactions. The process for production of polyester resin usually involves the combination of aromatic and unsaturated carboxylic acids or anhydrides with a polyol introduced as an oligomeric, prepolymer mixture. Terephthalic acid-containing UPRs are the most common for general purpose applications while isophthalic acid or bisphenol-based systems are utilized for higher value applications where superior thermal stability, mechanical properties and chemical resistance are desired. One promising system that minimizes the use of vinyl monomers employs a combination of maleic anhydride (MA), glycols and dicyclopentadiene (DCPD). (Chiu and Chen, 2001)

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