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4‐[Diphenyl(trimethylsilyl)methyl]benzophenone as initiator in the photopolymerization of methyl methacrylate and styrene
Author(s) -
Tasis Dimitrios A.,
Siskos Michael G.,
Zarkadis Antonios K.
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19980901)199:9<1981::aid-macp1981>3.0.co;2-g
Subject(s) - photopolymer , photoinitiator , benzophenone , polymerization , chemistry , polymer chemistry , methyl methacrylate , photochemistry , bulk polymerization , monomer , radical polymerization , styrene , polymer , copolymer , organic chemistry
The polymerization of methyl methacrylate (MMA) and styrene (St) has been studied using 4‐[diphenyl(trimethylsilyl)methyl]benzophenone 1 as photoinitiator. The polymerization follows a free radical mechanism; the polymerization rate increases linearly with the monomer concentration and was found to be proportional to the 0.33 and 1.40 power of the photoinitiator and the monomer (MMA) concentration, respectively. The overall activation energy in the case of MMA photopolymerization was calculated to be 25.0 kJ/mol. From 1 H NMR studies it is concluded that the obtained polymers contain two different trimethylsilyl moieties, one at the head and the other at the tail of the polymer chain, showing primary termination reactions even at low initiator concentrations. The p ‐benzoyltrityl radical 1 · is incorporated into the polymer chain to a very small extent, acting as a scavenger. This is also concluded by laser flash photolysis (LFP) and ESR spectroscopy measurements. A “living” character of the polymerization was observed only at very low initiator concentrations. The triplet state ( 3 1 * ) of the initiator was quenched by styrene, reducing its efficiency. The rate constant k q of the quenching process of 3 1 * was measured by LFP ( k q = 3.1 · 10 9 M −1 · S −1 ). The triplet state and the photodissociation efficiency of the initiator is unaffected by MMA at various concentrations.