Effect of hindered piperidine light stabilizer molecular structure and UV absorber addition on the oxidation of HDPE. Part 2: Mechanistic aspects—molecular modeling and electron spin resonance spectroscopy study

Abstract

AbstractThe first in this series of papers explored the effect of the structural characteristics of 2,2,6,6‐tetramethylpiperidine‐based hindered amine light stabilizers (HALS) on the thermal and photostabilization of high‐density polyethylene. In the second part, the energies (stabilities) of the nitroxyl radicals and various intermediate species have been predicted using AccuModel® and related to stabilization performance and electron spin resonance (ESR) spectral data. Nitroxyl radicals with low predicted stability generally afforded improved thermal and photostabilization. ESR spectra were used to obtain values of nitroxyl radical concentration ([>NO·]) and g‐factor as a function of pre‐aging time for combinations of pre‐aged HDPE and >NH HALS. Demethylation reactions of > N‐methyl HALS resulted in uselessly weak ESR spectra. The HALS that afforded poor thermal oxidative stabilization gave rise to pronounced minima in [>NO·] that coincided with a maximum in hydroperoxide concentration. The g‐factor values indicated that a predominant nitroxyl canonical form generally promoted superior thermal oxidative stabilization, whereas a predominance of the dipolar N·+O− form promoted superior photo‐oxidative stabilization. These trends may be related to greater radical‐scavenging and peroxide‐trapping effects, respectively. Molecular modeling and ESR spectra can therefore provide valuable insight into the effectiveness of HALS and stabilization mechanisms. J. Vinyl Addit. Technol. 10:159–167, 2004. © 2004 Society of Plastics Engineers.