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Abstract <p>For the first time, the controlled synthesis of poly(<i>N</i>-isopropylacrylamide) has been performed in supercritical carbon dioxide via reversible addition-fragmentation chain transfer radical polymerization in the temperature range of 55–70°C. It has been demonstrated that there is a range of CO<sub>2</sub> pressures (91–229&#xa0;bar), in which a polymer with a dispersity below 1.3 can be synthesized in the entire range of monomer conversions, with the number-average molecular weight of the polymer increasing linearly with conversion. As the pressure increases, control over the molecular weight characteristics of the polymer is lost due to separation of the system into two phases; the RAFT mechanism proceeds in one phase, and the conventional radical polymerization mechanism takes place in the second one. These patterns are characteristic of the three trithiocarbonates (dibenzyl trithiocarbonate, S,S'-bis(methyl-2-isobutyrate) trithiocarbonate, and (2‑dodecylthiocarbonothioylthio)-2-methylpropionic acid) and one dithiobenzoate (2-nitro-5-(2-propyl-yloxy)benzyl-4-cyano-4-phenylcarbonothioylthio)pentanoate) studied in the work.</p>

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Controlled Radical Polymerization of N-Isopropylacrylamide in Supercritical Carbon Dioxide

  • 期刊论文

  • 发表日期：

    2026年2月1日

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  • A. A. Popova,
  • V. F. Lisina,
  • A. V. Plutalova,
  • E. N. Golubeva,
  • E. V. Chernikova

摘要

Abstract

For the first time, the controlled synthesis of poly(N-isopropylacrylamide) has been performed in supercritical carbon dioxide via reversible addition-fragmentation chain transfer radical polymerization in the temperature range of 55–70°C. It has been demonstrated that there is a range of CO2 pressures (91–229 bar), in which a polymer with a dispersity below 1.3 can be synthesized in the entire range of monomer conversions, with the number-average molecular weight of the polymer increasing linearly with conversion. As the pressure increases, control over the molecular weight characteristics of the polymer is lost due to separation of the system into two phases; the RAFT mechanism proceeds in one phase, and the conventional radical polymerization mechanism takes place in the second one. These patterns are characteristic of the three trithiocarbonates (dibenzyl trithiocarbonate, S,S'-bis(methyl-2-isobutyrate) trithiocarbonate, and (2‑dodecylthiocarbonothioylthio)-2-methylpropionic acid) and one dithiobenzoate (2-nitro-5-(2-propyl-yloxy)benzyl-4-cyano-4-phenylcarbonothioylthio)pentanoate) studied in the work.