Styrene polymerization with a macroinitiator having siloxane units

Block copolymers containing segments of poly(dimethylsiloxane) (PDMS) and polystyrene were synthesized. Dihydroxy terminated PDMS M_n 2500 g/mol, was reacted with an ali-phatic diisocyanate (isophorone diisocyanate) and an aliphatic hydroperxide (t-butyl hy-droperoxide). The resulting polymeric peroxycarbamate having siloxane units (a new mac-roinitiator) was used as free radical initiator for vinyl polymerization of styrene. Formation of block copolymers was illustrated by several characterization methods such as chemical and spectroscopic analysis, fractionation, and GPC. Mechanical and thermal characterization of the copolymers were made by stress–strain tests and DSC. The surface properties and the morphology of the block copolymers were investigated by contact angle measurements and SEM. © 1996 John Wiley & Sons, Inc.