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Diphenyldiselenide As Novel Non–salt Photoinitiator for Photosensitized Cationic Polymerization of N‐Vinyl Carbazole
Author(s) -
Gupta Mukesh Kumar,
Singh Raj Pal
Publication year - 2006
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200650823
Subject(s) - cationic polymerization , photosensitizer , chemistry , photoinitiator , photochemistry , polymerization , carbazole , polymer chemistry , photopolymer , living cationic polymerization , radical polymerization , monomer , organic chemistry , polymer
Photoinitiated cationic polymerization of N‐vinyl carbazole (NVC) with diphenyldiselenide (DPDS) as an initiator and aromatic nitriles such as dicyanonaphthalene (DCN) and dicyanoanthracene (DCA) as sensitizer was studied at λ > 290 nm in CH 2 Cl 2 solvent using single electron transfer (SET) reactions in this investigation. Aromatic nitriles were found to be effective photosensitizer in initiating polymerization at wavelength λ > 290 nm where DPDS (λ max = 246 nm) do not absorb. However, the DPDS works well as an initiator with both DCN and DCA. An initiation mechanism is also proposed that involves the formation of selenium radical cation as actual initiating species. Upon photoirradiation, these radical cations are formed by single electron transfer between the excited singlet state sensitizer and the ground state of DPDS.