Copolymerization of acrylonitrile with 3‐chloro, 2‐hydroxy‐propyl acrylate and methacrylate

Acrylonitrile (AN) was copolymerized with 3‐chloro, 2‐hydroxy propyl acrylate (CHPA) and 3‐chloro, 2‐hydroxy‐propyl methacrylate (CHPMA) in water and water‐acetone medium at 40°C with potassium persulfate and sodium metabisulfite as redox initiators. Copolymer composition was determined from the nitrogen content. The reactivity ratios for the AN‐CHPMA system were also calculated by the Kelen–Tudos method. The reactivity ratio r2 (CHPMA) was higher for the AN‐CHPMA system in both media, which indicated higher reactivity of CHPMA toward the propagation species. Addition of acetone decreases r2 and increases r1. It was found that the copolymers prepared in water medium were not completely soluble in dimethylformamide (DMF); the insoluble fraction was rich in CHPA/CHPMA and increased with increasing comonomer composition. The influence of the acrylate comonomer on properties such as solubility and intrinsic viscosity was also studied.