Effect of ZnCl2 on the spontaneous copolymerization of methyl acrylate with substituted 1,3‐dienes

Abstract

AbstractThe reactions of the mildly electron‐poor olefin methyl acrylate (MA) with three electron‐rich substituted hydrocarbon 1,3‐dienes, namely 2,3‐dimethyl‐1,3‐butadiene (DMB), 4‐methyl‐1,3‐pentadiene (MPD) and isoprene (IP) were investigated in 1,2‐dichloroethane in the presence of various amounts of zinc chloride at different temperatures. ZnCl2 complexes with the ester group of MA and increases the MA's electron‐poor character and therefore its tendency towards reactions with electron‐rich dienes. In the absence of ZnCl2, no reaction occurs between the investigated dienes and MA under the used reaction conditions. Both alternating copolymers and [4+2] cycloadducts formed spontaneously in the presence of ZnCl2 even at room temperature. The structure of the diene and its nucleophilicity control the product distribution. For the DMB and IP systems, raising the reaction temperature and increasing the ZnCl2 concentration enhance the overall reaction rate and in most cases also favor the cycloaddition over the copolymerization. IP is less reactive than DMB. With MPD only copolymer is formed because the two terminal methyl groups retard the concerted [4+2] cycloaddition. These results are in agreement with a postulated mechanism involving competition between the formation of a π‐allyl 2‐hexene‐1,6‐diradical, capable of initiating free radical copolymerization, and concerted [4+2] Diels‐Alder cycloaddition.