Anionic polymerization of 2-(N,N-bistrimethylsilylaminomethyl)-1,3-butadiene and 2-(4-(N,N-bistrimethylsilylamino)butyl)-1,3-butadiene

Abstract

(cid:633) Anionic polymerization of two 1,3-butadiene derivatives containing trimethylsilyl-protected primary amino groups, 2-( N , N -bistrimethylsilylaminomethyl)-1,3-butadiene ( SA1Bd ) and 2-(4-( N , N -bistrimethylsilylamino)butyl)-1,3-butadiene ( SA4Bd ) were carried out under various conditions. When anionic polymerization of SA1Bd was attempted in cyclohexane at room temperature with using sec -BuLi as an initiator, no polymerization took place at all. Polystyrene having dienyl end group was obtained if anionic living polystyrene was used as an initiator, presumably due to the isomerization of carbanion accompanied with elimination of bistrimethylsilylamide anion. Such a side reaction was not observed in the anionic polymerization of SA4Bd . Polymer of predictable molecular weight with narrow molecular weight distributions was obtained in the polymerization in toluene. Microstructure of the resulting polymer was 86% 1,4-struc-ture though its geometry was not clear. Block copolymer with styrene was also obtained.