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

S. A. Kurochkin; Курочкин С. А.; L. I. Makhonina; Махонина Л. И.; E. O. Perepelitsina; Перепелицина Е. О.; M. L. Bubnova; Бубнова М. Л.; M. P. Berezin; Березин М. П.; V. P. Grachev; Грачев В. П.

doi:10.31857/S230811392370047X

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

Authors: Kurochkin S.A.¹^,2, Makhonina L.I.¹, Perepelitsina E.O.¹, Bubnova M.L.¹, Berezin M.P.¹, Grachev V.P.¹
Affiliations:
1. Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences
2. Bauman Moscow State Technical University
Issue: Vol 65, No 3 (2023)
Pages: 204-216
Section: ПОЛИМЕРИЗАЦИЯ
URL: https://journals.rcsi.science/2308-1139/article/view/135625
DOI: https://doi.org/10.31857/S230811392370047X
EDN: https://elibrary.ru/VYEPCV
ID: 135625

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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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