Anionic Polymerization of Polar Vinyl Monomers: Vinylpyridines, (Meth)acrylates, (Meth)acrylamides, (Meth)acrylonitrile, Phenyl Vinyl Sulfoxide, Benzofulvene, and Other Monomers

Abstract

The living anionic polymerizations of various polar vinyl monomers, such as vinylpyridines, acrylates, methacrylates, N,N-dialkylacrylamides, N,N-dialkylmethacrylamides, N-isopropylacrylamide, α-methylene-N-methylpyrrolidone, methacrylonitrile, vinyl sulfoxide, and benzofulvene, quantitatively proceeded and gave the polymers having predicted molecular weights and narrow molecular weight distributions. The effective anionic initiator systems were newly developed to prevent the inherent side reactions derived from the polar substituents during the polymerizations of these monomers. The stereospecific anionic polymerizations were realized for several monomers including methacrylates and N,N-dialkyl(meth)acrylamides by choosing the suitable initiator systems. The polar monomers possessing electron-withdrawing groups showed high anionic polymerizabilities, and the resulting living polymers had low nucleophilicities because of the stabilization effects of the substituents.