Abstract
AbstractThe copolymerization of acrylonitrile (AN) with sodium p‐styrenesulfonate (SSS) in dimethyl sulfoxide solution has been investigated. Monomer reactivity ratios at 45°C., for AN and SSS are found to be r1 = 0.15 ± 0.02, r2 = 0.55 ± 0.03. From these data Price Q and e values for SSS of 0.44 and −0.38, respectively, are calculated. The values are found to be different from those in aqueous solutions, which may be attributed to the different electron distributions in all solvents. Initial rates of copolymerization at 45°C. with azobisisobutyronitrile as initiator were determined over the entire range of composition from pure AN to pure SSS. It was found that there is a slight rise in copolymerization rates in the range of 90–95 mole‐% SSS in the monomer feed; this is attributed to the coexistence of liquids of different optical density. Homopolymerization of AN and SSS in dimethyl sulfoxide was also investigated and δ = (k/kp) for AN and SSS found to be 6.55 (mole‐sec./1.)½ and 2.46 (mole‐sec./1.)½, respectively. From these values the cross‐termination constant φ is calculated to be 6.5.
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