2-Cyanopropan-2-yl versus 1-Cyanocyclohex-1-yl Leaving Group: Comparing Reactivities of Symmetrical Trithiocarbonates in RAFT Polymerization

Oleksandr Ivanchenko, Maksym Odnoroh, Faustine Rolle, Asja A. Kroeger, Sonia Mallet-Ladeira, Stéphane Mazières, Marc Guerre, Michelle L. Coote, Mathias Destarac

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Abstract

This study introduces bis(1-cyanocyclohex-1-yl)trithiocarbonate (TTC-bCCH) as a novel trithiocarbonate chain transfer agent and compares its reactivity with the previously described bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St), n-butyl acrylate (nBA), and methyl methacrylate (MMA). Significant findings include the effective control of Mn and low dispersities from the onset of polymerization of St and nBA showing swift addition-fragmentation kinetics, leading to similar behaviors between the two RAFT agents. In contrast, a fourfold decrease of the chain transfer constant to MMA is established for TTC-bCCH over TTC-bCP. This trend is confirmed through density functional theory (DFT) calculations. Finally, the study compares thermoplastic elastomer properties of all-(meth)acrylic ABA block copolymers produced with both RAFT agents. The impact of dispersity of PMMA blocks on thermomechanical properties evaluated via rheological analysis reveals a more pronounced temperature dependence of the storage modulus (G′) for the triblock copolymer synthesized with TTC-bCCH, indicating potential alteration of the phase separation.

Original languageEnglish
Article number2400317
Number of pages9
JournalMACROMOLECULAR RAPID COMMUNICATIONS
Early online date4 Jun 2024
DOIs
Publication statusE-pub ahead of print - 4 Jun 2024

Keywords

  • DFT calculations
  • kinetics
  • RAFT
  • triblock copolymers
  • trithiocarbonate

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