Chemical modification of poly (methyl acrylate) via metalation and α - substitution

Poly(methyl acrylate) was transformed into polymers containing α-substituted units by a two-step reaction sequence involving formation of a poly(enolate) by base abstraction of the hydrogens located α to the ester carbonyl groups, followed by reaction of the poly(enolate) with electrophiles such as carbon dioxide, sulfur dioxide, or ethyl bromoacetate. Further modification of the α-carboxylate or α-sulfinate polymers led to poly(acrylates) bearing α-methyl carboxylate, α-methyl sulfone, or α-(2-hydroxyethyl sulfone) functional groups. Quenching of the poly(enolate) with ethyl bromoacetate gave a polymer containing itaconate as well as acrylate units. In general, the degree of functionalization achieved was from 0.3 to 0.65.