Abstract

The polymerization mechanism of acrylate initiated by methyl phenylglyoxylate was investigated. Matrix-assisted laser desorption/ionization time-of-flight mass spectra of the resultant polymer indicated that most polymers had either an acryloyl group or a benzoyl group as the initiating site. These results suggest that methyl phenylglyoxylate initiates polymerization by hydrogen abstraction from both a monomer and another initiator. These hydrogen abstraction-based polymerization reactions occur simultaneously but follow separate pathways. Polymers with acryloyl groups at both chain ends acted as cross-linkers in the subsequent polymerization involving gelation. Photopolymerization of dodecyl acrylate was conducted using methyl phenylglyoxylate as an initiator. Most polymers had either an acryloyl group or a benzoyl group at one of the chain ends. We investigated the initiation pathways and found out that methyl phenylglyoxylate initiated photopolymerization only by Norrish type II processes.

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