Construction of Vinyl Polymer and Polyester or Polyamide Units in a Single Polymer Chain via Metal-catalyzed Simultaneous Chain- and Step-growth Radical Polymerization of Various Monomers

Metal-catalyzed simultaneous chain-and step-growth radical polymerization was examined to combine common conjugated vinyl monomers, such as various acrylates and styrene, as chain-growth monomers and various ester-or amide-linked monomers bearing both an unconjugated C = C bond and an active C-Cl bond as step-growth monomers. The CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine-catalyzed copolymerization of alkyl acrylates and various step-growth monomers at a 1 : 1-monomer feed ratio resulted in almost linear random copolymers that consisted of vinyl polymer and polyester units. Additional functional groups, such as oxyethylene and disulfide units, can be introduced into the main chain using a step-growth monomer that possesses the functional units between the unconjugated C = C bond and the active C-Cl bond. Copolymerization at a higher feed ratio of chain-growth monomers, such as alkyl acrylates and styrene, can provide multiblock vinyl polymers connected to the functionalized step-growth monomer units.