Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect

Xiaojing Feng, Devendra S. Maurya, Nabil Bensabeh, Adrian Moreno, Takahiro Oh, Yuqing Luo, Jā Nis Lejnieks, Marina Galià, Yoshiko Miura, Michael J. Monteiro, Gerard Lligadas, Virgil Percec

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7 Citations (Scopus)

Abstract

The mixed-ligand system consisting of tris(2-aminoethyl)amine (TREN) and tris(2-dimethylaminoethyl)amine (Me6-TREN) during the Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) in "programmed" biphasic mixtures of the dipolar aprotic solvents NMP, DMF, and DMAc with H2O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo "click" reaction demonstrated that Me6-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu(II)Br2. Statistical analysis of the kinetic data together with control experiments demonstrated that this mixed-ligand effect enhanced the apparent rate constant of propagation, monomer conversion, and molecular weight control. The most efficient effect was observed at a 1/1 molar ratio between these two ligands, suggesting that in addition to a fast exchange between the two ligands, a new single dynamic ligand generated by hydrogen bonding may be responsible for the mixed ligand observed.

Original languageEnglish
Pages (from-to)250-261
Number of pages12
JournalBiomacromolecules
Volume21
Issue number1
DOIs
Publication statusPublished - Jan 13 2020

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biomaterials
  • Polymers and Plastics
  • Materials Chemistry

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