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Free radical copolymerization of styrene (S) and acrylonitrile (AN) in the ionic liquids (ILs) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF 6 ), 1,3-dimethylimidazolium dimethylphosphate ([MMIM]Me 2 PO 4 ) and 1-ethyl-3- methylimidazolium ethylsulfate ([EMIM]EtSO4) were investigated. 2,2’-azobisiso butyronitrile (AIBN) and dibenzoyl peroxide (BPO) were used as initiators and dimethyl formamide (DMF) and methanol as reference solvents. The influence of the viscosity on the conversion and the molecular weights was studied by variation of the reaction temperature and the IL concentration. At reaction temperatures of 80 - 85 °C already after 30 minutes a conversion of about 80 % and almost a doubling of the molecular weights is reached for the S/AN (50/50 mol%) copolymerization. In addition the copolymerization behavior of S/AN in [EMIM]EtSO 4  was investigated. With increasing concentration of AN in the monomer feed the polymerization rate as well as the molecular weights of the copolymers increase. The influence of the ionic liquid on the copolymer composition, glass-transition temperature and rheological behavior was studied.

Influence of Ionic Liquids on the Free Radical Copolymerization of Styrene with Acrylonitrile