Synthesis of Polyacrylonitrile-block-polystyrene copolymers by Atom Transfer Radical Polymerization” , Macr. Chem. Phys., 206, 1382-1388

The synthesis of polyacrylonitrile-block-polystyrene (PAN-b-PS) copolymers by atom transfer radical polymerization (ATRP) is reported. Chain extension of bromine terminated PAN macroinitiators with styrene was performed using a CuBr/N,N,N0,N00,N00-pentamethyldiethylenetriamine catalyst system and 2-cyanopyridine as a solvent. The first-order kinetic plots of styrene consumption showed a significant curvature, indicating a progressive decrease in the concentration of active species during copolymerization. The loss of the bromide end group was mainly ascribed to the elimination of HBr, as shown by 1H NMR spectroscopy. By varying the molar ratio of either the catalyst or the monomer to the initiator, a series of PAN-b-PS copolymers were prepared, with polydispersities as low as 1.3, and molar compositions ranging from 8.6/91.4 to 35.5/64.5.