Abstract
The photostability of polymeric materials is crucial for their applicability, especially under potentially harsh environmental conditions. In the current study, the influence of methyl-substitution on the photochemical stability of photoinitiator-derived benzoyl end groups is systematically investigated by a combination of pulsed-laser polymerization and subsequent size exclusion chromatography coupled with electrospray ionization mass spectrometry (PLP–SEC–ESI–MS), chemically induced dynamic nuclear polarization–nuclear magnetic resonance spectroscopy (CIDNP–NMR), and density functional theory (DFT) calculations. Poly(methyl methacrylate)s (pMMA) were synthesized employing benzoin-type photoinitiators with systematically substituted benzoyl moieties (i.e., 2-methylbenzoin, 3-methylbenzoin, 4-methylbenzoin, 2,4-dimethylbenzoin, 2,6-dimethylbenzoin, 2,4,6-trimethylbenzoin, 2,3,5,6-tetramethylbenzoin, and 2,3,4,5,6-pentamethylbenzoin). Photoinduced cleavage of the photoinitiator-based end group (irradiation...
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