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, Janis Lejnieks, Marina Galià, Yoshiko Miura, Michael J. Monteiro, Gerard Lligadas, Virgil Percec

Research output: Contribution to journalArticle

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 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
JournalBiomacromolecules
DOIs
Publication statusAccepted/In press - Jan 1 2019

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Living polymerization
Free radical polymerization
Ligands
Electrons
Amines
Weight control
Kinetics
Rate constants
Statistical methods
Hydrogen bonds
Monomers
Molecular weight
Nuclear magnetic resonance
Wire

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biomaterials
  • Polymers and Plastics
  • Materials Chemistry

Cite this

Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect. / Feng, Xiaojing; Maurya, Devendra S.; Bensabeh, Nabil; Moreno, Adrian; Oh, Takahiro; Luo, Yuqing; Lejnieks, Janis; Galià, Marina; Miura, Yoshiko; Monteiro, Michael J.; Lligadas, Gerard; Percec, Virgil.

In: Biomacromolecules, 01.01.2019.

Research output: Contribution to journalArticle

Feng, X, Maurya, DS, Bensabeh, N, Moreno, A, Oh, T, Luo, Y, Lejnieks, J, Galià, M, Miura, Y, Monteiro, MJ, Lligadas, G & Percec, V 2019, 'Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect', Biomacromolecules. https://doi.org/10.1021/acs.biomac.9b01282
Feng, Xiaojing ; Maurya, Devendra S. ; Bensabeh, Nabil ; Moreno, Adrian ; Oh, Takahiro ; Luo, Yuqing ; Lejnieks, Janis ; Galià, Marina ; Miura, Yoshiko ; Monteiro, Michael J. ; Lligadas, Gerard ; Percec, Virgil. / Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect. In: Biomacromolecules. 2019.
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AU - Lejnieks, Janis

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AU - Lligadas, Gerard

AU - Percec, Virgil

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