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Synthesis of functional fluorinated copolymers with different microstructure via reversible addition-fragmentation chain transfer (RAFT) process

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Abstract

Fluoropolymers are attractive due to their high resistance to external influences. However, they are poorly compatible with other materials (for example, paints and varnishes for the purpose of their hydrophobization). Compatibility can be improved by introducing hydrophilic monomer units. A convenient method is copolymerization with functional monomers. In this work, the method of controlled radical polymerization was chosen to resolve this problem, which makes it possible to obtain compositionally homogeneous samples of copolymers with reproducible properties. The reversible addition-fragmentation chain transfer (RAFT) polymerization of 2,2,2,3,3,4,4,5,5-octafluoropentylacrylate (OFPA), 1,1,1,3,3,3-hexafluoroisopropylacrylate (HFIPA), and glycidyl methacrylate (GMA) in the presence of 2-cyano-2-propyldodecyltritiocarbonate was first investigated. It was shown that CPDT is effective to control molecular weight characteristics of POFPA and GMA in concentration not more than 0.01 mol·L−1 and of PHFIPA − 0.03 mol·L−1. Copolymerization of fluorinated monomers (OFPA, HFIPA) and functional monomers (GMA) in the presence of low molecular (CPDT) and polymeric chain transfer agent was investigated. Reactivity ratios of monomers were determined by Fineman–Ross and Kelen–Tudos methods. The use of polymeric RAFT agent leads to instance of preferential solvation effect and formation of copolymer with gradient microstructure at final conversion in case of OFPA-GMA copolymerization. Thus, RAFT copolymerization of fluoroacrylates and GMA leads to formation of copolymers with block, gradient, or statistical microstructure that depended on synthesis condition. Block copolymers have amphiphilic properties and are able to form monomolecular films at the air/water interface. Further research will be aimed at modifying the resulting polymers using the epoxy group of GMA. This will make it possible to combine in one material both the properties of a surfactant (to stabilize acrylic dispersions) and a water repellent for paints.

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Funding

The work was supported by the Ministry of Science and Higher Education of the Russian Federation (the basic part of the state order, project № FSWR-2023-0025).

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  1. Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia

    Alexandra Grigoreva, Alexandra Vihireva & Sergey Zaitsev

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  1. Alexandra Grigoreva
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  2. Alexandra Vihireva
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  3. Sergey Zaitsev
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Correspondence to Alexandra Grigoreva.

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Grigoreva, A., Vihireva, A. & Zaitsev, S. Synthesis of functional fluorinated copolymers with different microstructure via reversible addition-fragmentation chain transfer (RAFT) process. Polym. Bull. (2024). https://doi.org/10.1007/s00289-023-05098-5

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  • DOI: https://doi.org/10.1007/s00289-023-05098-5

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