AbstractThe copolymerization of acrylonitrile (AN) with sodiump‐styrenesulfonate (SSS) in aqueous solutions (of pH 3 and pH 7) has been investigated. Monomer reactivity ratios at 45°C. for AN and SSS are found to ber1= 0.10 ± 0.02,r2= 1.20 ± 0.10 at pH 3 andr1= 0.05 ± 0.01,r2= 1.40 ± 0.04 at pH 7, from which PriceQandevalues for SSS of 0.76 and −0.26 at pH 3 and of 1.25 and −0.43 at pH 7 are calculated. Initial rates of copolymerization at 45°C. with ammonium persulfate (APS) as initiators were determined over the entire range of composition from pure AN to pure SSS, and it has been found that there is a sharp rise in copolymerization rates within 0.2–5 mole‐% monomer feed, sometimes being eight times larger than those in the neighboring range. The copolymerization in SSS monomer feed of 0.2–5 mole‐% occurs in the transition phase from homogeneous to heterogeneous, and the system is very viscous and slightly cloudy. From the investigation of the effect of initiator concentration on the copolymerization rate and the direct observation by an electron microscope, the sharp rise in copolymerization rates may reasonably be interpreted in terms of the emulsion copolym