Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates

Facile Access to Functional Materials

Emre H. Discekici, Athina Anastasaki, Revital Kaminker, Johannes Willenbacher, Nghia P. Truong, Carolin Fleischmann, Bernd Oschmann, David J. Lunn, Javier Read De Alaniz, Thomas P. Davis, Christopher M. Bates, Craig Jon Hawker

Research output: Contribution to journalArticleResearchpeer-review

49 Citations (Scopus)

Abstract

A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me6-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (D ≈ 1.1) and high end group fidelity, even at conversions greater than 95%. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.

Original languageEnglish
Pages (from-to)5939-5945
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number16
DOIs
Publication statusPublished - 26 Apr 2017

Cite this

Discekici, Emre H. ; Anastasaki, Athina ; Kaminker, Revital ; Willenbacher, Johannes ; Truong, Nghia P. ; Fleischmann, Carolin ; Oschmann, Bernd ; Lunn, David J. ; Read De Alaniz, Javier ; Davis, Thomas P. ; Bates, Christopher M. ; Hawker, Craig Jon. / Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates : Facile Access to Functional Materials. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 16. pp. 5939-5945.
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abstract = "A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me6-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (D ≈ 1.1) and high end group fidelity, even at conversions greater than 95{\%}. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.",
author = "Discekici, {Emre H.} and Athina Anastasaki and Revital Kaminker and Johannes Willenbacher and Truong, {Nghia P.} and Carolin Fleischmann and Bernd Oschmann and Lunn, {David J.} and {Read De Alaniz}, Javier and Davis, {Thomas P.} and Bates, {Christopher M.} and Hawker, {Craig Jon}",
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Discekici, EH, Anastasaki, A, Kaminker, R, Willenbacher, J, Truong, NP, Fleischmann, C, Oschmann, B, Lunn, DJ, Read De Alaniz, J, Davis, TP, Bates, CM & Hawker, CJ 2017, 'Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates: Facile Access to Functional Materials', Journal of the American Chemical Society, vol. 139, no. 16, pp. 5939-5945. https://doi.org/10.1021/jacs.7b01694

Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates : Facile Access to Functional Materials. / Discekici, Emre H.; Anastasaki, Athina; Kaminker, Revital; Willenbacher, Johannes; Truong, Nghia P.; Fleischmann, Carolin; Oschmann, Bernd; Lunn, David J.; Read De Alaniz, Javier; Davis, Thomas P.; Bates, Christopher M.; Hawker, Craig Jon.

In: Journal of the American Chemical Society, Vol. 139, No. 16, 26.04.2017, p. 5939-5945.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates

T2 - Facile Access to Functional Materials

AU - Discekici, Emre H.

AU - Anastasaki, Athina

AU - Kaminker, Revital

AU - Willenbacher, Johannes

AU - Truong, Nghia P.

AU - Fleischmann, Carolin

AU - Oschmann, Bernd

AU - Lunn, David J.

AU - Read De Alaniz, Javier

AU - Davis, Thomas P.

AU - Bates, Christopher M.

AU - Hawker, Craig Jon

PY - 2017/4/26

Y1 - 2017/4/26

N2 - A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me6-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (D ≈ 1.1) and high end group fidelity, even at conversions greater than 95%. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.

AB - A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me6-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (D ≈ 1.1) and high end group fidelity, even at conversions greater than 95%. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.

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U2 - 10.1021/jacs.7b01694

DO - 10.1021/jacs.7b01694

M3 - Article

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EP - 5945

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 16

ER -