High-molecular weight bottlebrushes via continuous flow photoiniferter polymerization of macromonomers

High-molecular weight amphiphilic PEG-based bottlebrushes have been synthesized via continuous flow photoiniferter polymerization of macromonomers using trithiocarbonates as chain transfer agents. Blue LED light-mediated polymerization of macromonomers under mild conditions (22–50 °C) resulted in th...

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Bibliographic Details
Published in:Polymer chemistry 2023-07, Vol.14 (27), p.3186-3195
Main Authors: Sivokhin, Alexey, Orekhov, Dmitry, Kazantsev, Oleg, Otopkova, Ksenia, Sivokhina, Olga, Chesnokov, Yuri, Smirnov, Michael, Ovchinnikov, Alexey, Makhov, Ilya
Format: Article
Language:English
Subjects:
Aqueous solutions
Chain transfer
Continuous flow
Copolymers
Micelles
Molecular weight
Phase transitions
Polymer chemistry
Polymerization
Toluene
Transmission electron microscopy
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Summary:High-molecular weight amphiphilic PEG-based bottlebrushes have been synthesized via continuous flow photoiniferter polymerization of macromonomers using trithiocarbonates as chain transfer agents. Blue LED light-mediated polymerization of macromonomers under mild conditions (22–50 °C) resulted in thermoresponsive copolymers with low dispersity and high yield. The effect of a solvent, temperature, comonomer composition and flow rate on the macromonomer conversions and solution properties of the copolymers have been investigated. The possibility of scaling the process to produce up to 54 g of pure polymer in an 8-hour day has been shown. Thermoresponsive properties of the bottlebrushes in aqueous solutions were studied by light scattering, turbidimetry and cryo-TEM. The samples synthesized in THF and toluene were compositionally homogeneous random copolymers with sharp reversible phase transitions while in DMSO, copolymers had broad thermoresponsive transitions. According to cryo-TEM, spherical unimolecular micelles at 10 °C transformed during LCST transition into tangled worm-like aggregates at 40 °C.
ISSN:1759-9954
1759-9962
DOI:10.1039/D3PY00042G