Photo-controlled Atom Transfer Radical Polymerization (Photo-ATRP) mediated by UV light (λ = 365 nm) was utilized, for the first time, to synthesize star polymers by arm-first method. Star diblock copolymers were prepared by a two-step process starting with a one pot amphiphilic diblock copolymer synthesis containing poly(oligo(ethylene glycol) methyl ether acrylate) (POEGA) blocks and poly(t-butyl acrylate) (PtBA) blocks. Star diblock copolymers were successfully prepared using various rigid and flexible crosslinkers using CuIIBr2/ Tris[2- (dimethylamino)ethyl]amine (Me6TREN) catalyst systems in trifluoroethanol (TFE) and CuIIBr2/tris(pyridin-2-ylmethyl)amine (TPMA) catalyst systems in water. Amphiphilic block copolymers POEGMA-b-PtBA form micelles in water by ultrasonication followed by crosslinking using photo-ATRP. Star-star coupling side reactions were minimized due to the preassembling of micelles. Very high molecular weight with narrow dispersity star diblock copolymers were obtained. After the deprotection of tert-butyl moieties, the star diblock copolymer will be utilized as nanoreactors in the future for fabricating functional metal nanoparticle (MNP) gels and superlattices.

Arm-first star polymer synthesis using photo-ATRP and their application towards nanoreactors for functional metal nanoparticle synthesis

ACS Spring 2022

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