Continuous flow synthesis of core cross-linked star polymers: Via photo-induced copper mediated polymerization

Jeroen H. Vrijsen, Camila Osiro Medeiros, Jonas Gruber, Tanja Junkers

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A convenient method to synthesize core cross-linked star polymers via a continuous flow photopolymerization process is developed. Photo-induced copper mediated radical polymerization was employed for arm and star syntheses. The arms of the core cross-linked star polymers are composed of poly(methyl acrylate) (with a Mn, arm of 2600 or 4700 g mol-1, Darm ≈ 1.12), and 1,4-butanediol diacrylate was used as the core cross-linker. Flow polymerization enables the rapid formation of star polymers (15-20 minutes, Mw, star flow = 170400 g mol-1, 33 arms). Furthermore, a reactor cascade was built that combines arm and star syntheses without the isolation of the intermediate product between both reactor stages. In this way, the star polymer is formed (Mw, star = 156500 g mol-1, 34 arms) in a one-pot fashion, yet under scalable conditions. Surface functionalized star polymers were obtained with similar molecular weights via alcohol-functional initiators. Finally, a flow reactor setup is demonstrated that allows direct access to miktoarm star polymers. In there, two different arms are synthesized from photopolymerization in parallel and then simultaneously fed into a third reactor. The resulting miktoarm core cross-linked star polymers are composed of poly(methyl acrylate) and poly(benzyl acrylate) arms (Mw, star = 189300 g mol-1, 33 arms). The reactor cascade enables rapid star polymer formation in a continuous process (within 40 minutes, when reactor conditions are stable) without intermediate purification, improved illumination and facile upscaling.

Original languageEnglish
Pages (from-to)1591-1598
Number of pages8
JournalPolymer Chemistry
Issue number13
Publication statusPublished - 7 Apr 2019

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