POLYMERIZATION OF MONOMERS CONTAINING FUNCTIONAL SILYL GROUPS - 13 - ANIONIC-POLYMERIZATION OF 2-[(N,N-DIALKYLAMINO)DIMETHYLSILYL]-1,3-BUTADIENE DERIVATIVES

Four 2-[(N,N-dialkylamino)silyl] substituted 1,3-butadiene derivatives , 2-[(N,N-diethylamino)dimethylsilyl]-1,3-butadiene (1), 2-[(N,N-dibut ylamino)dimethylsilyl]-1,3-butadiene (2), 2-[(1-pyrrolidinyl) dimethyl silyl]-1,3-butadiene (3), and )ethyl]-N-methylamino]dimethylsilyl]-1,3 -butadiene (4), were newly synthesized and polymerized under various c onditions of anionic polymerization. Under the condition of THF at -78 degrees C, all the monomers, 1-4, underwent living polymerization to afford the polymers of predictable molecular weights and narrow molecu lar weight distributions. On the other hand, side reactions occurred t o some extent in the polymerizations of 1-4 carried out in heptane at 40 degrees C, although yields of polymers were quantitative in all cas es within 1 h. The polymers obtained in THF consisted mainly of 1,4 (8 3-91%) and 1,2 (9-17%) linkages, while all the polymers obtained in he ptane were structurally pure 1,4-addition products. There were mixture s of 1,4-E (16-32%) and 1,4-Z (68-84%) structures in the polymers of 1 -3. The polymer of 4 was found to have a structure of exclusively 1,4- E unit.