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Extending the Scope of Bis(acyl)phosphane Oxides: Additional Derivatives
Author(s) -
Eibel Anna,
Schmallegger Max,
Zalibera Michal,
Huber Alex,
Bürkl Yasmin,
Grützmacher Hansjörg,
Gescheidt Georg
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700140
Subject(s) - chemistry , photochemistry , radical , flash photolysis , photopolymer , acrylate , styrene , intersystem crossing , monomer , quantum yield , electron paramagnetic resonance , radical polymerization , polymer chemistry , reaction rate constant , fluorescence , polymer , organic chemistry , copolymer , kinetics , physics , nuclear magnetic resonance , quantum mechanics , nuclear physics , singlet state , excited state
A series of new bis(acyl)phosphane oxide (BAPO) photoinitiators has been synthesized and tested with respect to their efficiency in the initiation step of radical photopolymerizations. The transient absorption spectra of the phosphanoyl radicals obtained upon laser‐flash photolysis reveal maxima at ca. 450–460 nm. Rate constants for the addition of these radicals to the double bonds of butyl acrylate, methyl methacrylate, 1‐vinyl‐2‐pyrrolidone, and styrene have been determined. All phosphanoyl radicals have been found to react the most rapidly with styrene and the most slowly with butyl acrylate. Low fluorescence quantum yields of 0.1–0.3 % reveal that the studied BAPOs undergo efficient intersystem crossing, followed by α‐cleavage. The heat profiles of selected photopolymerizations have been observed using a high‐resolution infrared camera. Thermal‐imaging experiments show substantial monomer‐dependent exothermicity. All BAPO derivatives can additionally act as electron acceptors, as indicated by cyclic voltammetry and EPR spectroscopy.