Abstract: | Atom transfer radical polymerization has been used to prepare well-defined vinyl macromonomers of polystyrene using vinyl chloroacetate as an initiator. Because styrene and vinyl chloroacetate do not copolymerize, no branching or incorporation of the initiator into the backbone was observed. Macromonomers of several molecular weights were prepared and copolymerized free radically with N-vinylpyrrolidinone in varying feed ratios in order to produce poly(NVP-g-Sty) graft copolymers. The macromonomers used were of sufficiently high molecular weight to form physical crosslinks in solvents which favor the hydrophilic NVP, such as water, which prevent the copolymer from dissolving and cause it to swell. These materials, therefore, formed hydrogels of swellabilities in water exceeding 95%, depending on the amount of styrene that was incorporated into the copolymer. Limitations of and alternatives to this method are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 823–830, 1998 |