Visible Light-Induced Grafting from Polyolefins

Polyethylene-graft-poly(tert-butylacrylate) (PE-g-PtBA) copolymers were prepared by using a combination of ring-opening metathesis polymerization (ROMP), hydrobromination, and visible light-induced free radical polymerization. First, cis-cyclooctene was polymerized via ROMP in the presence of a chain transfer agent and quantitatively hydrobrominated. Poly-(tert-butyl acrylate) (PtBA) chains were then grown via a grafting from approach from the Br-substituted linear poly(ethylene) (PE) backbone using dimanganese decacarbonyl (Mn-2(CO)(10)) under visible light. The effect of Mn-2(CO)(10) concentration and irradiation time on the grafting density and efficiency was evaluated. The tert-butyl acrylate (tBA) esters of the graft copolymers were hydrolyzed into acrylic acid functionalities by acidolysis to obtain hydrophilic polyolefins. The precursor polymer, graft copolymer, and hydrolyzed polymer were characterized by H-1 and C-13 NMR, Fourier transform infrared, atomic force microscopy, and contact angle measurements.