Model systems for poly(acrylic acid) main-chain radicals based on the Kemp's triacid framework.
Kemp's triacid (KTA) and cyclohexane tricarboxylic acid (CTA) are small-molecule model systems for acrylic acid polymers, having the same functionalities and stereoregularities as isotactic poly(methacrylic acid) (PMAA) and poly(acrylic acid) (PAA), respectively. As part of an ongoing investigation of radicals produced by photolysis of acrylic polymers, the photochemistry and free radicals from the model systems have been studied using time-resolved EPR spectroscopy as a function of temperature and pH. Radicals are created by direct photolysis of the acids at 248 nm or by sensitized photo-oxidation using quinone triplet states at 308 nm. The two methods of radical production lead to different chemically induced electron spin polarization (CIDEP) patterns in the ensuing radicals, which are simulated and discussed. Well-resolved spectra are obtained at all temperatures for the model system radicals, which are determined to be in the slow motion condition. DFT calculations of the model system radicals are presented and discussed in support of the experimental data.
Lebedeva
Natalia V
NV
Caudill Laboratories, CB # 3290, Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
Gorelik
Elena V
EV
Prowatzke
Adam M
AM
Forbes
Malcolm D E
MD