Dye‐sensitized photopolymerization. I. Polymerization of acrylamide in aqueous solution sensitized by methylene blue–triethanolamine system

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Abstract
The polymerization of aqueous acrylamide induced by visible light in the presence of methylene blue–triethanolamine as the sensitizing system has been investigated. The polymerization was found to follow a nonsteady‐state kinetic scheme. The rate was proportional to the first power of the absorbed light intensity and approximately proportional to the initial monomer concentration. The rate passed through a maximum as a function of the initial dye concentration. The molecular weights of the polymers were in the range of one million. The molecular weights were independent of the absorbed light intensity, essentially directly proportional to the initial monomer concentration, and decreased logarithmically with the initial dye concentration. Both spectroscopy and polymerization behavior suggest that the monomeric form of the dye is a photosensitizer while the associated form is a chain terminator. The kinetic chains were terminated unimolecularly, and the molecular weights were governed by a chain transfer process.

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