Electron spin resonance in polyphenylacetylene

Abstract

By polymerizing phenylacetylene in the absence of initiator and in vacuo while observing electron spin resonance, it was established that the paramagnetism in the thermal polymer (PPA-T) cannot be due to interaction with oxygen but must be a property of the chemically uncontaminated macromolecule. The ESR behavior of a concentrated solution of PPA(T) in monomer and of solid (amorphous) PPA(T) displays a Curie dependence, whereas the ESR absorption of crystalline polymer made with coordination catalysts increases by one to two orders of magnitude over the temperature of about 60 to 140°C. The major portion of the XRD crystallinity disappears more sharply, at about 120°C. The paramagnetism in PPA must therefore be associated with “conformational defects” in the individual macromolecules.