Comestible curcumin: From kitchen to polymer chemistry as a photocatalyst in metal-free ATRP of (meth)acrylates

Abstract

The article presents an application of curcumin, a widely available and cost-effective organic dye, to control visible-light mediated ATRP. A two-component photocatalytic system composed of curcumin and an amine-based electron donor activates alkyl bromide and controls radical polymerizations by a reductive quenching pathway. The polymerizations of various types of (meth)acrylates were performed under blue LED irradiation (λmax = 460 nm, 5 mW cm−2). The effect of electron donor type, solvent, photocatalyst and electron donor concentration, target degree of polymerization (DPtarget) etc. on the metal-free ATRP of methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (OEGMA500) was systematically investigated to optimize the polymerization conditions. Moreover, comestible curcumin of four different brands available in the market as kitchen spices was used, which makes this approach economical (∼0.04 € for 15 g of turmeric). In order to increase the applicability of the curcumin-based polymerization strategy, the concept was extended to the polymerization of other methacrylates – butyl methacrylate (nBMA), di(ethylene glycol) methyl ether methacrylate (DEGMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), and acrylates i.e. poly(ethylene glycol) methyl ether acrylate (OEGA480), n-butyl acrylate (nBA) and 2-hydoxyethyl acrylate (HEA). In situ chain extension experiment demonstrated the preservation of chain-end functionality, enabling the facile synthesis of well-controlled copolymers.