A new macromonomeric initiator (macroinimer) was synthesized and evaluated for the bulk polymerization of styrene at 60 and 80 degrees C. The macroinimer containing poly(dimethylsiloxane), PDMS, was synthesized via condensation reactions between 4,-4'-azobis-4-cyanopentanoyl chloride (ACPC), PDMS and methacryloyl chloride. The product (MIM I) was thermally homopolymerized and copolymerized with styrene in bulk. Kinetics of radical polymerization of styrene with MIM I at 60 degrees C and at low conversion was studied. Rate constant K, k(p)(fk(d)/k(1))(1/2), was estimated from kinetic data as 1.15 x 10(-4) 1(1/2) mol(-1/2) s. Bulk polymerization of styrene with macroinimers at 80 degrees C gave crosslinked block copolymers. D.s.c. measurements showed that crosslinked block copolymers had a glass transition temperature around 45 degrees C. This is evidence of a plasticizing effect of flexible polysiloxane segments in copolymers. Crosslinked PDMS-b-PS block copolymers obtained using macroinimers may be an interesting group of thermoplastic elastomers. (C) 1997 Elsevier Science Ltd.