Living Anionic Polymerization of 4-Trimethylstannylstyrene

The living anionic polymerization of 4-trimethylstannylstyrene in tetrahydrofuran at -78 degrees C, initiated with sec-butyllithium, is achieved for the first time. Unwanted side reactions, such as the nucleophilic attack of a carbanion to the stannyl group, may be suppressed through the equimolar addition of dibutylmagnesium (Bu2Mg) to the initiator. The suppression of side reactions allows the control of the molecular weight of poly(4-trimethylstannylstyrene) and maintains low molar-mass dispersity (D-M) values of less than 1.1. By increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a highly controllable polymerization reaction. Controlled syntheses of block and statistical copolymers derived from styrene and 4-trimethylstannylstyrene are successfully developed due to the similar nucleophilicity of their living chain termini.