Photosensitized Polymerizations of Styrene and Methyl Methacrylate by Tetraphenylphosphonium Salts

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Abstract
Tetraphenylphosphonium salts with anions such as Cl−, Br−, and BF− 4 have been shown to be photoinitiators of styrene (St) and methyl methacrylate (MMA). These polymerizations were inhibited by the addition of benzoquinone as a radical scavenger. Copolymerization of St and MMA by tetraphenylphosphonium tetrafluoroborate showed typical monomer reactivity ratios of a free-radical mechanism. Further, photodecomposition of tetraphenylphosphonium bromide in cyclohexene produced phenylcyclohexane and bicyclohexenyl. These results indicate that photolysis of these phosphonium salts gave the phenyl radical, which initiated the free-radical polymerizations of St and MMA. On the other hand, tetraphenylphosphonium iodide did not initiate the photopolymerization of vinyl monomers.

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