Abstract: | The alternating copolymerization of styrene and methyl α-chloroacrylate (MCA) with diethylaluminum chloride (Et2AlCl) in benzene at 0°C has been investigated. The copolymer has an equimolar composition irrespective of the feed monomer composition, the copolymer yield and the amount of Et2AlCl used. The copolymerization proceeds first very rapidly and then rather slowly after attaining a certain yield which varies proportionally to the amount of Et2AlCl used. A maximum copolymer yield is observed at about 60% MCA feed composition. The 1H-NMR analyses of dyad, triad, and pentad of the alternating deuterated α-d-St-MCA copolymer indicate that the configuration of this copolymer can be explained by a single parameter, coisotacticity σ(σ = 0.69). A favorable mechanism of the alternating propagation as well as of the stereoregularity control is discussed. |