Random and Diblock Thermoresponsive Oligo(ethylene glycol)-Based Copolymers Synthesized via Photo-Induced RAFT Polymerization. 2021

Alexey Sivokhin, and Dmitry Orekhov, and Oleg Kazantsev, and Olga Sivokhina, and Sergey Orekhov, and Denis Kamorin, and Ksenia Otopkova, and Michael Smirnov, and Rostislav Karpov
Laboratory of Acrylic Monomers and Polymers, Department of Chemical and Food Technologies, Dzerzhinsk Polytechnic Institute, Nizhny Novgorod State Technical University n.a. R.E. Alekseev, 24 Minin Street, 603950 Nizhny Novgorod, Russia.

Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that blue and green LED light could initiate RAFT polymerization of macromonomers without an exogenous initiator at room temperature, giving bottlebrush polymers with low dispersity at sufficiently high conversions achieved in 1-2 h. The pseudo-living mechanism of polymerization and high chain-end fidelity were confirmed by successful chain extension. Thermoresponsive properties of the copolymers in aqueous solutions were studied via turbidimetry and laser light scattering. Random copolymers of methoxy- and alkoxy oligo(ethylene glycol) methacrylates of a specified length formed unimolecular micelles in water with a hydrophobic core consisting of a polymer backbone and alkyl groups and a hydrophilic oligo(ethylene glycol) shell. In contrast, the diblock copolymer formed huge multimolecular micelles.

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