Direct controlled polymerization of ionic monomers by surface-initiated ATRP using a fluoroalcohol and ionic liquids

Motoyasu Kobayashi, Masami Terada, Yuki Terayama, Moriya Kikuchi, Atsushi Takahara

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Surface-initiated atom transfer radical polymerization (ATRP) of (2-methacryloyloxyethyl)trimethylammonium chloride (MTAC), 3-(N-2- methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate) (MAPS), and 2-methacryloyloxyethyl phosphorylcholine (MPC) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3- methylimidazolium chloride at 60 °C to produce well-defined ionic polymer brushes and the corresponding free polymers with predictable number-average molecular weight (M n, 1×10 4-3×10 5 g mol -1) and narrow molecular weight dispersity (M w/M n<1.2). A first-order kinetic plot for ATRP of MTAC and MAPS revealed a linear relationship between the monomer conversion index (ln([M] 0/[M])) and polymerization time. Reduction in polymerization rates was observed with an increase in ionic liquid concentration. The M n of both poly(MTAC) and poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the M n of the polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated.

Original languageEnglish
Pages (from-to)364-374
Number of pages11
JournalIsrael Journal of Chemistry
Volume52
Issue number3-4
DOIs
Publication statusPublished - Apr 1 2012

Fingerprint

Ionic Liquids
Atom transfer radical polymerization
Polymers
Monomers
Polymerization
Trifluoroethanol
Chlorides
Brushes
Molecular weight
Methacrylates
Copper
Ligands
Catalysts
Kinetics
Substrates

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Direct controlled polymerization of ionic monomers by surface-initiated ATRP using a fluoroalcohol and ionic liquids. / Kobayashi, Motoyasu; Terada, Masami; Terayama, Yuki; Kikuchi, Moriya; Takahara, Atsushi.

In: Israel Journal of Chemistry, Vol. 52, No. 3-4, 01.04.2012, p. 364-374.

Research output: Contribution to journalArticle

Kobayashi, Motoyasu ; Terada, Masami ; Terayama, Yuki ; Kikuchi, Moriya ; Takahara, Atsushi. / Direct controlled polymerization of ionic monomers by surface-initiated ATRP using a fluoroalcohol and ionic liquids. In: Israel Journal of Chemistry. 2012 ; Vol. 52, No. 3-4. pp. 364-374.
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AB - Surface-initiated atom transfer radical polymerization (ATRP) of (2-methacryloyloxyethyl)trimethylammonium chloride (MTAC), 3-(N-2- methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate) (MAPS), and 2-methacryloyloxyethyl phosphorylcholine (MPC) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3- methylimidazolium chloride at 60 °C to produce well-defined ionic polymer brushes and the corresponding free polymers with predictable number-average molecular weight (M n, 1×10 4-3×10 5 g mol -1) and narrow molecular weight dispersity (M w/M n<1.2). A first-order kinetic plot for ATRP of MTAC and MAPS revealed a linear relationship between the monomer conversion index (ln([M] 0/[M])) and polymerization time. Reduction in polymerization rates was observed with an increase in ionic liquid concentration. The M n of both poly(MTAC) and poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the M n of the polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated.

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