Controlled Radical Polymerization of an Acrylamide Containing l-Phenylalanine Moiety via RAFT

Abstract

Homopolymers of a monosubstituted acrylamide having an amino acid moiety in the side chain, N-acryloyl-l-phenylalanine methyl ester (A-Phe-OMe), have been synthesized by reversible addition−fragmentation chain transfer (RAFT) polymerization. Two dithioesters were used as chain transfer agents: benzyl 1-pyrrolecarbodithioate (CTA 1) and benzyl dithiobenzoate (CTA 2). The controlled character of the polymerization in the presence of CTA 1 in dioxane at 60 °C was confirmed by the formation of narrow polydispersity products, the molecular weight controlled by the monomer/CTA molar ratio, the linear relationship between the molecular weight and conversion, and the ability to increase the molecular weight by a second addition of monomer. Poly(A-Phe-OMe) with controlled molecular weight, low polydispersity, and enhanced isotacticity was also prepared by RAFT polymerization in the presence of catalytic amounts of Lewis acid, Y(OTf)3. The RAFT polymerizations of A-Phe-OMe in methanol at 45 °C and in methanol−tolu...