Protection and polymerization of functional monomers, 14. Anionic living polymerization of 4‐[N,N‐bis(trimethylsilyl)‐aminomethyl]styrene and 4‐{2‐[N,N‐bis(trimethylsilyl)amino]ethyl}styrene

Abstract Anionic polymerization of 4‐[ N , N ‐bis(trimethylsilyl)aminomethyl]styrene ( 1 ) and 4‐{2‐[ N , N ‐bis(trimethylsilyl)amino]ethyl}styrene ( 2 ) were carried out at −78°C in tetrahydrofuran (THF)/pentane mixtures with butyllithium, oligo(α‐methylstyryl)lithium, oligo(α‐methylstyryl)potassium, and cumylpotassium. Polymerizations of 1 and 2 proceed without chain transfer and termination reactions to give stable “living polymers” when butyllithium or oligo(α‐methylstyryl)lithium are used as initiator. The resulting polymers have predictable molecular weights and narrow molecular weight distributions (ratio of weight‐ to number‐average molecular weights, M̄ w / M̄ n = 1,04–1,14). Under mild acidic conditions (pH 3–5 in THF/water), cleavage of the NSi bonds in the polymers is completely achieved to give well‐defined poly(4‐aminomethyl)styrene and poly[4‐(2‐aminoethyl)styrene]. The triblock copolymers of polystyrene‐ block ‐poly( 1 )‐ block ‐polystyrene and polystyrene‐ block ‐poly( 2 )‐ block ‐polystyrene are readily prepared in quantitative yields by sequential polymerization of styrene with living poly( 1 ) or living poly( 2 ).