2‐Cyanopropan‐2‐yl versus 1‐Cyanocyclohex‐1‐yl Leaving Group: Comparing Reactivities of Symmetrical Trithiocarbonates in RAFT Polymerization - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Macromolecular Rapid Communications Année : 2024

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

Faustine Rolle
  • Fonction : Auteur
Asja Kroeger

Résumé

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 ( n BA), and methyl methacrylate (MMA). Significant findings include the effective control of M n and low dispersities from the onset of polymerization of St and n BA 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.

Domaines

Chimie
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Dates et versions

hal-04698384 , version 1 (16-09-2024)

Identifiants

Citer

Oleksandr Ivanchenko, Maksym Odnoroh, Faustine Rolle, Asja Kroeger, Sonia Mallet-Ladeira, et al.. 2‐Cyanopropan‐2‐yl versus 1‐Cyanocyclohex‐1‐yl Leaving Group: Comparing Reactivities of Symmetrical Trithiocarbonates in RAFT Polymerization. Macromolecular Rapid Communications, 2024, ⟨10.1002/marc.202400317⟩. ⟨hal-04698384⟩
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