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On the Absence of Cyclic Structures in Branched Polystyrenes Synthesized by Living Three-Dimensional Radical Polymerization in the Medium of a Deteriorating Thermodynamic Quality Solvent

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Abstract

Branched polystyrenes are synthesized by the radical copolymerization of styrene and divinylbenzene with reversible inhibition (in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl) under deteriorating thermodynamic quality of the solvent. The resulting polymers are studied by size-exclusion chromatography combined with static light scattering, ozonolysis, NMR spectroscopy, and differential scanning calorimetry. The branched polymers synthesized by living radical polymerization are characterized by lower intrinsic viscosity values than their linear analogs. Kuhn–Mark–Houwink parameters for these polymers in a tetrahydrofuran solution (а = 0.29) confirm the nonlinear architecture of macromolecules and a high content of pendant double bonds comparable in the order of magnitude with their theoretical content in the absence of the cyclization reaction indicate their branched structure. The glass transition temperature of the branched polystyrenes is 20–35°С lower than the glass transition temperature of the linear polystyrene.

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ACKNOWLEDGMENTS

This work was performed using equipment of the Analytical Center for Collective Use of the Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences (no. 40607).

Funding

This work was carried out in accordance with the theme of the State Assignment (State Registration number АААА-А19-119041090087-4).

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Authors and Affiliations

  1. Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 142432, Chernogolovka, Moscow oblast, Russia

    S. A. Kurochkin, L. I. Makhonina, E. O. Perepelitsina, M. L. Bubnova, M. P. Berezin & V. P. Grachev

  2. Bauman Moscow State Technical University, 105005, Moscow, Russia

    S. A. Kurochkin

Authors
  1. S. A. Kurochkin
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  2. L. I. Makhonina
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  3. E. O. Perepelitsina
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  4. M. L. Bubnova
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  5. M. P. Berezin
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  6. V. P. Grachev
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Correspondence to S. A. Kurochkin.

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Translated by T. Soboleva

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Kurochkin, S.A., Makhonina, L.I., Perepelitsina, E.O. et al. On the Absence of Cyclic Structures in Branched Polystyrenes Synthesized by Living Three-Dimensional Radical Polymerization in the Medium of a Deteriorating Thermodynamic Quality Solvent. Polym. Sci. Ser. B 65, 284–293 (2023). https://doi.org/10.1134/S1560090423700938

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  • DOI: https://doi.org/10.1134/S1560090423700938

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