Propylene Radical Copolymerization with Vinyl Acetate, Methyl Acrylate, Dimethyl Maleate, and Diethyl Fumarate

Abstract

Abstract Propylene (Pr) radical copolymerization (in water emulsion) with vinyl acetate (VAc), methyl acrylate (MA), dimethyl maleate (DMM), and diethyl fumarate (DEF) has been studied and is discussed, together with literature data on other Pr radical copolymerization reactions. Composition diagrams of the systems studied are presented. Pr relative activity is determined primarily by polarity and to a lesser degree by resonance stabilization of the comonomers as described by the “Q-e” scheme. Pr reacts actively and gives alternating copolymers when comonomer has relatively high electronegativity (e > 1.2) and low resonance stabilization (e.g., DMM, tetrafluoro-ethylene, maleic anhydride). A decrease of comonomer electronegativity (e.g., VAc, vinyl chloride) and/or an increase of resonance stabilization (e.g., MA, DEF, acrylonitrile) result in a noticeable decrease of Pr activity and in a lower Pr concentration in the copolymers as compared to the comonomer mixture. The mechanism of these effects is discu...