Graft Copolymerization of Acrylonitrile onto Polystyrene

It is possible to graft vinyl monomers, such as acrylonitrile, onto polystyrene via anionic processes but not by a radical process. Both homopolymerization of the added acrylonitrile and graft copolymerization in which acrylonitrile units are added to the para position on the benzene ring in styrene occur; the conversion of acrylonitrile into polymer depends upon the time and temperature of the reaction and on the concentration of the anionic initiator, butyllithium. A constant 15–20% of the acrylonitrile is converted to graft copolymer while the remainder is homopolymerized; graft copolymer may be separated from homopolymer by selective precipitation from either N,N′‐dimethylformamide or aqueous potassium thiocyanate. Treatment of the mixed graft and homopolymer with aqueous sodium hydroxide converts the nitrile into an acid salt and one may conveniently separate homopolymer from graft copolymer in this way. Each polystyrene chain is grafted with acrylonitrile units