Interfacial energy promotes radical heterophase polymerization

Experimental evidence is presented that during the conditions of aqueous heterophase polymerization radical generation and subsequent polymerization are induced by the interfacial energy. A comprehensive study of the emulsion polymerization of styrene at 25°C with various types of emulsifiers and with different nonredox initiators such as potassium peroxodisulfate, 2,2′-azoisobutyronitrile, dibenzoyl peroxide, and poly(ethylene glycol)-azo-initiator reveals that the particular initiator-stabilizer combination has a strong influence on the achievable final conversion and the latex properties. The deceleration of the polymerization due to the low temperature allowed the recognition of basic differences in the behavior of monomer- and water-soluble initiators, especially at low conversions during the prenucleation period.