ANIONIC-POLYMERIZATION OF MONOMERS CONTAINING FUNCTIONAL-GROUPS .4. ANIONIC LIVING POLYMERIZATION OF N,N-DIALKYL-4-VINYLBENZENESULFONAMIDES

Anionic polymerizations of NN-dimethyl-4-vinylbenzenesulfonamide (6a), NN-diethyl-4-vinylbenzenesulfonamide (6b), and N-methyl-N-[(4-vinylphenyl)sulfonyl]piperazine (6c) were carried out at -78-degrees-C in tetrahydrofuran. The initiators included potassium naphthalenide, oligo(alpha-methylstyryl)dilithium, -disodium, and -dipotassium, (1,1,4,4-tetraphenylbutanediyl)dilithium and -dipotassium, [1,1-bis-[(4'-(trimethylsilyl)phenyl]hexyl]lithium, and [1,1,4,4-tetrakis[4'-(trimethylsilyl)phenyl]butanediyl]dipotassium. These polymerizations gave poly(6)s in quantitative yields. In all cases, the obtained polymers had narrow molecular weight distributions (M(w)BAR/M(n)BAR < 1.15) and molecular weights predicted from the molar ratio of monomer to initiator, indicating that the anionic polymerizations of these monomers gave stable living polymers. Novel block copolymers, poly(6b-b-styrene-b-6b), poly(6b-b-isoprene-b-6b), poly(6b-b-2-vinylpyridine-b-6b), poly(2-vinylpyridine-b-6b-b-2-vinylpyridine), poly(methyl methacrylate-b-6b-b-methyl methacrylate), poly(tert-butyl methacrylate-b-6b-b-tert-butyl methacrylate), and poly(6c-b-styrene-b-6c) were synthesized using these living systems.