Several new macroinitiators and macromerinitiators (macroinimers) were synthesized and evaluated for the bulk polymerization of styrene at 60-degrees-C. Macroinitiators were prepared from the reaction of 4,4'-dicyano-4,4' azovaleryl chloride (1) with poly(ethylene glycol) (PEG) with a M(w) of 400 and with either benzoyl chloride, acetyl chloride, phenyl isocyanate, or poly(ethylene glycol) oleyl ether. Macromer initiators were also prepared from the reaction of 1 with PEG having M. values of 200,400,600, 1000, or 1500 and with 4-vinylbenzyl chloride. The bulk polymerization of styrene by macroinimers gave crosslinked styrene-PEG block copolymers, while the polymerization by macroinitiators gave soluble copolymers. The molecular weights of the styrene-PEG block copolymers obtained with macroinitiators having either oleyl, benzoyl, or phenyl urethane end groups were 22000-29000 g/mol. DSC measurements showed that the crosslinked block copolymers had crystalline PEG units with melting transitions ranging from 11-37-degrees-C. (C) 1994 John Wiley & Sons, Inc.